Science.gov

Sample records for hydrogen isotope adsorption

  1. CRYOGENIC ADSORPTION OF HYDROGEN ISOTOPES OVER NANO-STRUCTURED MATERIALS

    SciTech Connect

    Xiao, S.; Heung, L.

    2010-10-07

    Porous materials such as zeolites, activated carbon, silica gels, alumina and a number of industrial catalysts are compared and ranked for hydrogen and deuterium adsorption at liquid nitrogen temperature. All samples show higher D{sub 2} adsorption than that of H{sub 2}, in which a HY sample has the greatest isotopic effect while 13X has the highest hydrogen uptake capacity. Material's moisture content has significant impact to its hydrogen uptake. A material without adequate drying could result in complete loss of its adsorption capacity. Even though some materials present higher H{sub 2} adsorption capacity at full pressure, their adsorption at low vapor pressure may not be as good as others. Adsorption capacity in a dynamic system is much less than in a static system. A sharp desorption is also expected in case of temperature upset.

  2. Breakthrough curve analysis of pressure swing adsorption for hydrogen isotope separation

    SciTech Connect

    Kotoh, K.; Tanaka, M.; Sakamoto, T.; Nakamura, Y.; Asakura, Y.; Uda, T.; Sugiyama, T.

    2008-07-15

    For the purpose of developing an effective system for hydrogen isotope separation, we have been studying the adsorption-desorption dynamic behavior of hydrogen and deuterium in a packed-bed column with synthetic zeolites, aimed at applying the pressure swing adsorption process. The adsorption behavior of molecules in the packed-bed is reflected in the breakthrough curves. To understand the characteristic behaviors of hydrogen isotopes in the packed-bed, we carried out breakthrough experiments in a conventional adsorption process and in a practical process following sequential processes alternating between adsorption and desorption. From the former experiments, the results were obtained that the overall mass transfer was influenced by longitudinal dispersion relating to the superficial velocity and that the process governing the mass transfer within adsorbents was diffusion in the macro-pores of pellets. In the latter experiments, unique profile breakthrough curves were observed. These curves can be described with the numerical simulation assuming the initial distributions in a packed-bed. (authors)

  3. Correlation of adsorption isotherms of hydrogen isotopes on mordenite adsorbents using reactive vacancy solution theory

    SciTech Connect

    Munakata, K.; Nakamura, A.; Kawamura, Y.

    2015-03-15

    The authors have applied the isotherm equations derived from the reactive vacancy solution theory (RVST) to correlation of experimental and highly non-ideal adsorption isotherms of hydrogen and deuterium on a mordenite adsorbent, and have examined the ability of the isotherm equations to match this correlation. Several isotherm equations such as Langmuir, Freundlich, Toth, Vacancy Solution Theory and so forth were also tested, but they did not work. For the Langmuir-Freundlich equation tests have indicated that its 'ability to correlate' of the adsorption isotherms is not satisfactory. For the multi-site Langmuir-Freundlich (MSLF) equation the correlation of the isotherms appears to be somewhat improved but remains unsatisfactory. The results show that the isotherm equations derived from RVST can better correlate the experimental isotherms.

  4. HYDROGEN ISOTOPE TARGETS

    DOEpatents

    Ashley, R.W.

    1958-08-12

    The design of targets for use in the investigation of nuclear reactions of hydrogen isotopes by bombardment with accelerated particles is described. The target con struction eomprises a backing disc of a metal selected from the group consisting of molybdenunn and tungsten, a eoating of condensed titaniunn on the dise, and a hydrogen isotope selected from the group consisting of deuterium and tritium absorbed in the coatiag. The proeess for preparing these hydrogen isotope targets is described.

  5. Chromatographic hydrogen isotope separation

    DOEpatents

    Aldridge, Frederick T.

    1981-01-01

    Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, 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.

  6. Chromatographic hydrogen isotope separation

    DOEpatents

    Aldridge, F.T.

    Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, 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 cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

  7. Adsorption and coadsorption of molecular hydrogen isotopes in zeolites. II. Infrared analyses of H2, HD, and D2 in NaA

    NASA Astrophysics Data System (ADS)

    Stéphanie-Victoire, Françoise; de Lara, Evelyne Cohen

    1998-10-01

    The infrared analysis of the induced bands of molecular hydrogen isotopes, adsorbed in NaA zeolite, shows several features; (i) when the amount of adsorbed molecules increases, the bands become complex, showing three components, which can be related to different energetic situation of the molecules in the cavity; (ii) the band frequency is lower than the gas frequency; for each species the shifts are proportional to the inverse square root of the mass (same interaction with the crystal); (iii) the absolute intensity increases when the temperature decreases, this is due to the fact that the molecule remains longer in the vicinity of the adsorption site where the electric field is the highest. Its amplitude is deduced from the absolute intensities measured at the lowest temperature (˜1010 V/m, in agreement with other results).

  8. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

    An apparatus and method for determining the concentrations of hydrogen isotopes in a sample. Hydrogen in the sample is separated from other elements using a filter selectively permeable to hydrogen. Then the hydrogen is condensed onto a cold finger or cryopump. The cold finger is rotated as pulsed laser energy vaporizes a portion of the condensed hydrogen, forming a packet of molecular hydrogen. The desorbed hydrogen is ionized and admitted into a mass spectrometer for analysis.

  9. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  10. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  11. Container for hydrogen isotopes

    DOEpatents

    Solomon, David 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. 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.

  12. Hydrogen Adsorption in Carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Cabrera, A. L.; Rojas, S.; Dias-Droguett, D. E.; Bhuyan, H.; Aomoa, N.; Kakati, M.

    2013-03-01

    We have studied hydrogen adsorption in carbon nanoparticles using a quartz crystal microbalance. The carbon nanoparticles were synthesized from a thermal plasma jet at different pressure (15 - 263 torr) of the reactants and different current (50 - 250 A) to generate the plasma. The as-prepared carbon nanoparticles were directly deposited on top of the gold electrode of a quartz crystal and we monitored in-situ the changes in resonance frequency while the chamber was pressurized at different hydrogen pressures. These changes enabled determination of absorbed hydrogen mass in order to get H/C mass ratio curves as a function of H2 pressure. Adsorption curves obtained in some carbon nanoparticles indicated the formation of hydrogen monolayer inside the pores of the carbon nanoparticles. Using the value of the jump due to the formation of a H2\\ monolayer, a surface area was estimated between 40-60 m2/g for hydrogen adsorption. In other carbon samples, hydrogen uptake curves indicated that H2 was filling the sample's pores when pore volume was large. These observations will be discussed in detail for several carbon nanoparticles samples. Funds provided by VRI Puente 9/2012 and 10/2012

  13. Hydrogen adsorption on and solubility in graphites

    SciTech Connect

    Kanashenko, S.L.; Gorodetsky, A.E.; Chernikov, V.N.; Markin, A.V.; Zakharov, A.P.

    1995-12-01

    The experimental data on sorption and solubility of hydrogen isotopes in graphite in a wide ranges of temperature and pressure are reviewed. The Langmuir type adsorption is proposed for the hydrogen -- graphites interaction with taking into account dangling sp{sup 2}{minus}bonds relaxation. Three kinds of traps are proposed: Carbon interstitial loops with the adsorption enthalpy of {minus}4.4 eV/H{sub 2} (Traps l); carbon network edge atoms with the adsorption enthalpy of {minus}2.3 eV/H{sub 2} (Traps 2): Basal planes adsorption sites with enthalpy of +2.43 eV/H{sub 2} (Traps 3). The sorption capacity of every kind of graphite could be described with its own unique set of traps. The number of potential sites for the ``true solubility`` (Traps 3) we assume as 1E+6 appm, or HC=l, but endothermic character of this solubility leads to negligible amount of inventory in comparison with Traps 1 and Traps 2. The irradiation with neutrons or carbon atoms increases the number of Traps 1 and Traps 2. At damage level of {approximately}1 dpa under room temperature irradiation the number of these traps was increased up to 1500 and 5000 appm respectively. Traps 1 and Traps 2 are stable under high temperature annealing.

  14. Cascades for hydrogen isotope separation using metal hydrides

    SciTech Connect

    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.

  15. Apparatus and process for separating hydrogen isotopes

    DOEpatents

    Heung, Leung K; Sessions, Henry T; Xiao, Xin

    2013-06-25

    The apparatus and process for separating hydrogen isotopes is provided using dual columns, each column having an opposite hydrogen isotopic effect such that when a hydrogen isotope mixture feedstock is cycled between the two respective columns, two different hydrogen isotopes are separated from the feedstock.

  16. Hydrogen adsorption on functionalized nanoporous activated carbons.

    PubMed

    Zhao, X B; Xiao, B; Fletcher, A J; Thomas, K M

    2005-05-12

    There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.

  17. Hydrogen isotope separation

    DOEpatents

    Bartlit, John R.; Denton, William H.; Sherman, Robert H.

    1982-01-01

    A system of four cryogenic fractional distillation columns interlinked with two equilibrators for separating a DT and hydrogen feed stream into four product streams, consisting of a stream of high purity D.sub.2, DT, T.sub.2, and a tritium-free stream of HD for waste disposal.

  18. Hydrogen isotope separation

    DOEpatents

    Bartlit, J.R.; Denton, W.H.; Sherman, R.H.

    Disclosed is a system of four cryogenic fractional distillation columns interlinked with two equilibrators for separating a DT and hydrogen feed stream into four product streams, consisting of a stream of high purity D/sub 2/, DT, T/sub 2/, and a tritium-free stream of HD for waste disposal.

  19. Interactions of Hydrogen Isotopes and Oxides with Metal Tubes

    SciTech Connect

    Glen R. Longhurst

    2008-08-01

    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.

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

    SciTech Connect

    Hindin, Saul G.; Roberts, George W.

    1980-08-12

    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.

  1. Hydrogen-isotope permeation barrier

    DOEpatents

    Maroni, Victor A.; Van Deventer, Erven H.

    1977-01-01

    A composite including a plurality of metal layers has a Cu-Al-Fe bronze layer and at least one outer layer of a heat and corrosion resistant metal alloy. The bronze layer is ordinarily intermediate two outer layers of metal such as austenitic stainless steel, nickel alloys or alloys of the refractory metals. The composite provides a barrier to hydrogen isotopes, particularly tritium that can reduce permeation by at least about 30 fold and possibly more below permeation through equal thicknesses of the outer layer material.

  2. Apparatus for storing hydrogen isotopes

    DOEpatents

    McMullen, John W.; Wheeler, Michael G.; Cullingford, Hatice S.; Sherman, Robert H.

    1985-01-01

    An improved method and apparatus for storing isotopes of hydrogen (especially tritium) are provided. The hydrogen gas(es) is (are) stored as hydrides of material (for example uranium) within boreholes in a block of copper. The mass of the block is critically important to the operation, as is the selection of copper, because no cooling pipes are used. Because no cooling pipes are used, there can be no failure due to cooling pipes. And because copper is used instead of stainless steel, a significantly higher temperature can be reached before the eutectic formation of uranium with copper occurs, (the eutectic of uranium with the iron in stainless steel forming at a significantly lower temperature).

  3. Advanced Mass Spectrometers for Hydrogen Isotope Analyses

    SciTech Connect

    Chastagner, P.

    2001-08-01

    This report is a summary of the results of a joint Savannah River Laboratory (SRL) - Savannah River Plant (SRP) ''Hydrogen Isotope Mass Spectrometer Evaluation Program''. The program was undertaken to evaluate two prototype hydrogen isotope mass spectrometers and obtain sufficient data to permit SRP personnel to specify the mass spectrometers to replace obsolete instruments.

  4. Chromium stable isotope fractionation during adsorption

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

    Chromium is a common anthropogenic contaminant in ground water. 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 control Cr mobility in aqueous solutions with Cr(VI) reduction to Cr(III) controlling the attenuation of Cr in groundwater. Our previous study demonstrated that abiotic Cr(VI) reduction causes an isotope fractionation of -3.5 permil (53Cr/52Cr) and isotopes can therefore be used to calculate the extent of reduction. In the present study, experiments were conducted to measure Cr isotope fractionation during Cr(VI) sorption on Al203. Sorption of Cr(VI) could be important as a small isotope fractionation may get amplified along the edges of a Cr(VI) contaminated plume. A previous study demonstrated a similar process with Fe isotopes on anion exchange resin. Initial solutions of 200 mg/l Cr(VI) (as K2Cr2O7) and 0.1 mM KCl were made up. Sufficient solid Al203 was added to achieve 50% sorption. After equilibration, the solution was extracted by centrifuging and filtering with a 0.2 micron filter. Al203 was then added again to result in a further 50% sorption of the remaining Cr(VI). This process was repeated 10 times to amplify any isotopic fractionation between dissolved and adsorbed Cr(VI). The instantaneous stable isotope fractionation was calculated based on the δ 53Cr values of the initial and final Cr(VI) solutions. The results show that the stable isotope values measured in the solutions after the ten steps were within the uncertainty of the isotope value of the initial solution. Therefore, no significant stable isotope fractionation occurred. We are presently conducting experiments with goethite and expect similar results. Therefore, any fractionation of chromium stable isotopes observed in contaminant plumes are a result of processes other than adsorption (i.e., reduction).

  5. Zn isotope fractionation during adsorption on birnessite

    NASA Astrophysics Data System (ADS)

    Bryan, A. L.; Dong, S.; Wasylenki, L. E.

    2013-12-01

    The biogeochemical cycling of zinc (Zn), an important micronutrient in the ocean, may influence primary productivity and species composition within surface waters. The chemical speciation and bioavailability of Zn is governed by diverse abiotic and biotic processes. These processes include adsorption reactions at mineral/water interfaces, as nanoparticles of oxyhydroxide minerals are known to adsorb significant amounts of Zn in surface waters (and during formation of ferromanganese crusts). Investigation of Zn isotope fractionation caused by adsorption onto birnessite, the dominant manganese oxide mineral in ferromanganese crusts, may help to explain the enrichment of heavy Zn isotopes in ferromanganese crusts. This will provide insight into the role of adsorption of Zn to nanoparticulate minerals in surface waters and into the overall biogeochemical cycling of Zn. This work aims to determine the mechanism and magnitude of Zn isotope fractionation during adsorption onto synthetic birnessite (KMn2O4.1.5H2O). Our simple-system experiments involve mixing solutions of 130 ppb Zn with aliquots of birnessite suspension (proportions varied to give a range of surface coverage) and a fixed pH near that of seawater at ~8.5. The mixtures react for 48 hours. The recovered dissolved Zn and adsorbed Zn are then separated, purified, and analyzed isotopically on a Nu Plasma MC-ICP-MS. Preliminary results show enrichment of light Zn isotopes on the mineral surfaces (Δ66/64Znsorbed-aqueous = -0.3‰). A time series will reveal whether this process is governed by equilibrium or Rayleigh fractionation. Contrary to our results, previously published studies led us to hypothesize that isotopically heavy Zn would adsorb compared to co-existing dissolved Zn. Maréchal et al. (2000) recorded ferromanganese crusts that were heavier than seawater with a mean δ66Zn value of 0.90‰. Dissolved Zn is octahedrally coordinated with oxygen atoms, but an EXAFS study by Manceau et al. (2002

  6. Zinc isotope fractionation during adsorption on calcite

    NASA Astrophysics Data System (ADS)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (δ66/64Zn from -0.1 to 0.5‰), but modern ferromanganese crusts (δ66/64Zn from 0.5 to 1.2‰), as well as carbonates (δ66/64Zn from 0.3 to 1.4‰), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with Δ68/66Zncalcite-solution of approximately 0.3‰. The variation of Δ68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a

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

    SciTech Connect

    Willms, R.S.

    1993-12-01

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

  8. Tracing food webs with stable hydrogen isotopes.

    PubMed

    Estep, M F; Dabrowski, H

    1980-09-26

    The hydrogen isotopic content of an animal's food, not water, determines that animal's hydrogen isotopic content. Liver and muscle tissue from mice reared on a diet such that the ratio of deuterium to hydrogen (DIH) of their food and water was kept constant, have the same average D/H ratio as the food source. In a simple, natural population of snails and their possible algal diets, Littorina obtusata (northern Atlantic intertidal snails that feed almost exclusively on the brown alga Fucus vesiculosus) has the same D/H ratio as Fucus vesiculosis and not that of the other algae available to the snails.

  9. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    HEUNG, LEUNGK.

    2004-08-18

    Porous solids such as activated alumina, silica and molecular sieves generally contain significant amounts of hydrogen atoms in the form of H2O or OH even at high temperature and low humidity environment. A significant amount of this hydrogen is available for reversible isotopic exchange. This exchange reaction is slow under normal conditions and does not render itself to practical applications. But if the exchange kinetics is improved this reaction has the potential to be used for tritium removal from gas streams or for hydrogen isotopic separation.The use of catalysts to improve the exchange kinetics between hydrogen isotope in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum or palladium as the catalyst. The granules were packed in a 2-cm diameter column for isotope exchange tests. Gas streams containing different concentrations of deuterium in nitrogen or argon were fed through the protium saturated column. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  10. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1991-05-08

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using, a metal hydride.

  11. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1993-03-30

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

  12. Hydrogen isotope separation installation for tritium facility

    SciTech Connect

    Andreev, B.M.; Perevezentsev, A.N.; Selivanenko, I.L.; Tenyaev, B.N.; Vedeneev, A.I.; Golubkov, A.N.

    1995-10-01

    The separation of hydrogen isotopes in the hydrogen-palladium system in sectioned separation columns with the simulation of counter-current isotopic exchange is described. The separation efficiency of sectioned columns is investigated with the experimental installation as a function of various parameters. The separation of deuterium-tritium mixtures with high tritium concentrations is tested with the pilot installation operating at room temperature and atmospheric hydrogen pressure. Due to very high separation efficiency, flexibility and simplicity of operation separation installations with sectioned columns are ideally suitable for tritium laboratories and facilities dealing with separation of hydrogen isotopes. Estimation of applicability of sectioned columns for regeneration of exhaust gas in a fuel cycle of thermonuclear reactors, such as JET and ITER, shows the number of advantages of separation installations with sectioned columns. 12 refs., 3 figs., 2 tabs.

  13. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, James W.

    1993-01-01

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

  14. Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111).

    PubMed

    Koitaya, Takanori; Shimizu, Sumera; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2012-06-07

    Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.

  15. Apparatus for separating and recovering hydrogen isotopes

    DOEpatents

    Heung, Leung K.

    1994-01-01

    An apparatus for recovering hydrogen and separating its isotopes. The apparatus includes a housing bearing at least a fluid inlet and a fluid outlet. A baffle is disposed within the housing, attached thereto by a bracket. A hollow conduit is coiled about the baffle, in spaced relation to the baffle and the housing. The coiled conduit is at least partially filled with a hydride. The hydride can be heated to a high temperature and cooled to a low temperature quickly by circulating a heat transfer fluid in the housing. The spacing between the baffle and the housing maximizes the heat exchange rate between the fluid in the housing and the hydride in the conduit. The apparatus can be used to recover hydrogen isotopes (protium, deuterium and tritium) from gaseous mixtures, or to separate hydrogen isotopes from each other.

  16. Apparatus for separating and recovering hydrogen isotopes

    SciTech Connect

    Heung, L.K.

    1994-05-17

    An apparatus is described for recovering hydrogen and separating its isotopes. The apparatus includes a housing bearing with at least a fluid inlet and a fluid outlet. A baffle is disposed within the housing, attached thereto by a bracket. A hollow conduit is coiled about the baffle, in spaced relation to the baffle and the housing. The coiled conduit is at least partially filled with a hydride. The hydride can be heated to a high temperature and cooled to a low temperature quickly by circulating a heat transfer fluid in the housing. The spacing between the baffle and the housing maximizes the heat exchange rate between the fluid in the housing and the hydride in the conduit. The apparatus can be used to recover hydrogen isotopes (protium, deuterium and tritium) from gaseous mixtures, or to separate hydrogen isotopes from each other. 2 figures.

  17. Hydrogen Isotope Exchange Properties of Porous Solids Containing Hydrogen

    SciTech Connect

    Heung, L.K.; Staack, G.C.

    2005-07-15

    The use of catalysts to improve the exchange kinetics between hydrogen isotopes in the gas phase and that in the solid phase was investigated. Granules of alumina, silica and molecular sieve were coated with platinum as the catalyst. The granules saturated with water at room humidity were packed in a 2-cm diameter column for isotope exchange tests. Deuterium and protium were alternately fed through the column at a constant rate. Isotope concentration in column effluent was monitored to generate isotope break-through curves. The curves were analyzed to produce information on the kinetics and capacity of the material. The results showed that all materials tested provided some extent of isotope exchange but some were superior both in kinetics and capacity. This paper will present the test results.

  18. A Study of Hydrogen Adsorption in Pretreated Nanocarbon

    DTIC Science & Technology

    2003-01-01

    UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP014294 TITLE: A Study of Hydrogen Adsorption in Pretreated Nanocarbon ...Materials Research Society 112•3 A Study of Hydrogen Adsorption in Pretreated Nanocarbon Sang Moon Lee, Satoshi Ohshima, Kunio Uchida and Motoo Yumura

  19. Review of Hydrogen Isotope Permeability Through Materials

    SciTech Connect

    Steward, S. A.

    1983-08-15

    This report is the first part of a comprehensive summary of the literature on hydrogen isotope permeability through materials that do not readily form hydrides. While we mainly focus on pure metals with low permeabilities because of their importance to tritium containment, we also give data on higher-permeability materials such as iron, nickel, steels, and glasses.

  20. Charge induced enhancement of adsorption for hydrogen storage materials

    NASA Astrophysics Data System (ADS)

    Sun, Xiang

    2009-12-01

    The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage

  1. Hydrogen adsorption in metal-decorated silicon carbide nanotubes

    NASA Astrophysics Data System (ADS)

    Singh, Ram Sevak; Solanki, Ankit

    2016-09-01

    Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

  2. METHOD OF SEPARATING HYDROGEN ISOTOPES

    DOEpatents

    Salmon, O.N.

    1958-12-01

    The process of separating a gaseous mixture of hydrogen and tritium by contacting finely dlvided palladium with the mixture in order to adsorb the gases, then gradually heating the palladium and collecting the evolved fractlons, is described. The fraction first given off is richer in trltium than later fractions.

  3. Isotope effects of hydrogen and atom tunnelling

    NASA Astrophysics Data System (ADS)

    Buchachenko, A. L.; Pliss, E. M.

    2016-06-01

    The abnormally high mass-dependent isotope effects in liquid-phase hydrogen (deuterium) atom transfer reactions, which are customarily regarded as quantum effects, are actually the products of two classical effects, namely, kinetic and thermodynamic ones. The former is determined by the rate constants for atom transfer and the latter is caused by nonbonded (or noncovalent) isotope effects in the solvation of protiated and deuterated reacting molecules. This product can mimic the large isotope effects that are usually attributed to tunnelling. In enzymatic reactions, tunnelling is of particular interest; its existence characterizes an enzyme as a rigid molecular machine in which the residence time of reactants on the reaction coordinate exceeds the waiting time for the tunnelling event. The magnitude of isotope effect becomes a characteristic parameter of the internal dynamics of the enzyme catalytic site. The bibliography includes 61 references.

  4. Isotope tracer study of hydrogen spillover on carbon-based adsorbents for hydrogen storage.

    PubMed

    Lachawiec, Anthony J; Yang, Ralph T

    2008-06-17

    A composite material comprising platinum nanoparticles supported on molecular sieve templated carbon was synthesized and found to adsorb 1.35 wt % hydrogen at 298 K and 100 atm. The isosteric heat of adsorption for the material at low coverage was approximately 14 kJ/mol, and it approached a value of 10.6 kJ/mol as coverage increased for pressures at and above 1 atm. The increase in capacity is attributed to spillover, which is observed with the use of isotopic tracer TPD. IRMOF-8 bridged to Pt/C, a material known to exhibit hydrogen spillover at room temperature, was also studied with the hydrogen-deuterium scrambling reaction for comparison. The isotherms were reversible. For desorption, sequential doses of H2 and D2 at room temperature and subsequent TPD yield product distributions that are strong indicators of the surface diffusion controlled reverse spillover process.

  5. Hydrogen adsorption on sulphur-doped SiC nanotubes

    NASA Astrophysics Data System (ADS)

    Sevak Singh, Ram

    2016-07-01

    Hydrogen (H2) is an energy carrier and clean fuel that can be used for a broad range of applications that include fuel cell vehicles. Therefore, development of materials for hydrogen storage is demanded. Nanotubes, in this context, are appropriate materials. Recently, silicon carbide nanotube (SiCNTs) have been predicted as potential nanomaterials for hydrogen storage, and atomic doping into the nanotubes improves the H2 adsorption. Here, we report H2 adsorption properties of sulphur-doped (S-doped) SiCNTs using first-principles calculations based on density functional theory. The H2 adsorption properties are investigated by calculations of energy band structures, density of states (DOS), adsorption energy and Mulliken charge population analysis. Our findings show that, compared to the intrinsic SiCNT, S-doped SiCNT is more sensitive to H2 adsorption. H2 gas adsorption on S-doped C-sites of SiCNT brings about significant modulation of the electronic structure of the nanotube, which results in charge transfer from the nanotube to the gas, and dipole-dipole interactions cause chemisorptions of hydrogen. However, in the case of H2 gas adsorption on S-doped Si-sites of the nanotube, lesser charge transfer from the nanotube to the gas results in physisorptions of the gas. The efficient hydrogen sensing properties of S-doped SiCNTs, studied here, may have potential for its practical realization for hydrogen storage application.

  6. Challenges in hydrogen adsorptions: from physisorption to chemisorption

    NASA Astrophysics Data System (ADS)

    Ding, Feng; Yakobson, Boris I.

    2011-06-01

    In this short review, we will briefly discuss the story of hydrogen storage, its impact on clean energy application, especially the challenges of using hydrogen adsorption for onboard application. After a short comparison of the main methods of hydrogen storage (high pressure tank, metal hydride and adsorption), we will focus our discussion on adsorption of hydrogen in graphitic carbon based large surface area adsorbents including carbon nanotubes, graphene and metal organic frameworks. The mechanisms, advantages, disadvantages and recent progresses will be discussed and reviewed for physisorption, metal-assisted storage and chemisorption. In the last section, we will discuss hydrogen spillover chemisorption in detail for the mechanism, status, challenges and perspectives. We hope to present a clear picture of the present technologies, challenges and the perspectives of hydrogen storage for the future studies.

  7. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  8. Collision integrals for isotopic hydrogen molecules.

    NASA Technical Reports Server (NTRS)

    Brown, N. J.; Munn, R. J.

    1972-01-01

    The study was undertaken to determine the effects of reduced mass and differences in asymmetry on the collision integrals and thermal diffusion factors of isotopic hydrogen systems. Each system selected for study consisted of two diatoms, one in the j = 0 rotation state and the other in the j = 1 state. The molecules interacted with a Lennard-Jones type potential modified to include angular terms. A set of cross sections and collision integrals were obtained for each system.

  9. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  10. Collision integrals for isotopic hydrogen molecules.

    NASA Technical Reports Server (NTRS)

    Brown, N. J.; Munn, R. J.

    1972-01-01

    The study was undertaken to determine the effects of reduced mass and differences in asymmetry on the collision integrals and thermal diffusion factors of isotopic hydrogen systems. Each system selected for study consisted of two diatoms, one in the j = 0 rotation state and the other in the j = 1 state. The molecules interacted with a Lennard-Jones type potential modified to include angular terms. A set of cross sections and collision integrals were obtained for each system.

  11. Biogeochemistry of the stable hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Estep, Marilyn F.; Hoering, Thomas C.

    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 dependant. 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 %. 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%.) 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%. In addition, the organically bonded H in nonsaponifiable lipids was further fractionated by -80%. 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.

  12. Selenium isotope fractionation during adsorption onto the modified clay minerals

    NASA Astrophysics Data System (ADS)

    Xu, W.; Jianming, Z.; Tan, D.; Qin, H.

    2016-12-01

    Currently, Selenium (Se) isotopes have been used as a paleoenvironmental proxy to trace Se evolution in Ancient Ocean. And many researchers considered the variation of Se isotopes in nature mainly result from the reduction of Se oxyanion, while Se isotope fractionation during adsorption onto minerals was rarely reported. Therefore, based on the previous studies [1, 2], we used three common clay minerals in supergene environment: montmorillonite, illite and kaolinite as an adsorbent to study Se isotope fractionation during adsorption. Before doing adsorption experiments, the adsorbent were modified as Na-clay minerals to remove the possibility of interference of Ca2+, Fe3+, Fe2+ as well as organic matters. A batch adsorption experiments were carried out at room temperature (23 ±2 °) under N2 atmosphere, initial Se concentration (SeO32-/ SeO42-) was respectively 200ng and 100ng, the solution ionic strength was 0.1mol/L NaCl; the ratio of liquid to solid is 2g / L, and pH = 5. Experimental results showed that adsorption reached a steady state during 48h, and the maximum adsorption for SeO32- was larger than SeO42-. The isotope data showed that SeO42- adsorbed onto three clay minerals didn't present obvious Se isotope fractionation, generally δ82/78Se is less than 0.1 ‰. Meanwhile, SeO32- during adsorption process also didn't show the significant fractionation, less than 0.3 ‰. However, interestingly, for SeO32- the δ82/78Se values of solution during adsorption onto kaolinite underwent a process of increasing by 0.5‰ compared to the initial solution and then decreasing to 0.3‰. We speculated the reason may not be related to the surface charge of the clay minerals, but mostly with the layered structure of clay minerals. Montmorillonite and illite are 2: 1; kaolinite is 1: 1 layered structure. The different layered structure may influence the isotope fraction between Se oxyanions and clay minerals. These still needs further and more experiments to definitely

  13. Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

    NASA Technical Reports Server (NTRS)

    Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

    1998-01-01

    Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

  14. Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

    NASA Technical Reports Server (NTRS)

    Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

    1998-01-01

    Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

  15. Hydrogen isotope separation utilizing bulk getters

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1990-12-11

    This patent describes hydrogen isotope separation utilizing bulk getters. Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

  16. Isotopic tracing of hydrogen transport and trapping in nuclear materials

    NASA Astrophysics Data System (ADS)

    Chêne, Jacques; Martin, Frantz

    2017-06-01

    Some illustrations of the use of deuterium or tritium for isotopic tracing of hydrogen absorption, transport and trapping in nuclear materials are presented. Isotopic tracing of hydrogen has been shown to be successful for the determination of the boundaries conditions for hydrogen desorption or absorption in a material exposed to a hydrogen source. Also, the unique capabilities of isotopic tracing and related techniques to characterize H interactions with point defects and dislocations acting as moving traps has been demonstrated. Such transport mechanisms are considered to play a major role in some stress corrosion cracking and hydrogen embrittlement mechanisms. This article is part of the themed issue 'The challenges of hydrogen and metals'.

  17. Hydrogen isotope fractionation in methane plasma

    NASA Astrophysics Data System (ADS)

    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.

  18. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

    Knize, R.J.; Cecchi, J.L.

    1991-08-20

    Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen. 4 figures.

  19. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    1990-01-01

    Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

  20. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    1991-01-01

    Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

  1. Hydrogen isotope fractionation in methane plasma

    PubMed Central

    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. PMID:28096422

  2. Hydrogen isotope fractionation in methane plasma.

    PubMed

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

    2017-01-31

    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.

  3. Atomic hydrogen adsorption on a Stone Wales defect in graphite

    NASA Astrophysics Data System (ADS)

    Letardi, Sara; Celino, Massimo; Cleri, Fabrizio; Rosato, Vittorio

    2002-01-01

    Ab initio electronic structure calculations have been used to evaluate the binding energy of atomic hydrogen to graphite lattice defects. Results show that carbon sites belonging to a Stone-Wales defect are preferred binding sites with respect to undefected sites. Upon hydrogen adsorption, carbon sites undergo a sizeable tetragonalization effect which is more pronounced on the defected sizes.

  4. Periodicity in the isotope chemistry of hydrogen

    PubMed Central

    Bigeleisen, Jacob

    1981-01-01

    Periodicities and regularities are established among the deuterium to protium isotopic reduced partition function ratios, ln(s/s′)f, of 39 diatomic and 19 polyatomic hydrides. It is shown that ln(s/s′)f for diatomic hydrides can be correlated with the position in the periodic table of the element X in the hydride HX. A similar analysis is made for the contributions from X—H stretching motion in the polyatomic hydrides HnX. It is shown that the contributions from stretching motions to ln(s/s′)f in diatomic and polyatomic molecules are a linear function of the square root of the stretching force constants. The contributions from bending coordinates to ln(s/s′)f depend on both the molecular structure of the hydride and the bending force constant. Simple correlations are established for the bending contributions to ln(s/s′)f for the hydrides of the elements belonging to a common group in the periodic table. Four periodic rules of the isotope chemistry of hydrogen summarize and classify the data on the isotopic partition function ratios and the isotopic differences in free energies of formation of hydrides. PMID:16593077

  5. Isotope microscopy visualization of the adsorption profile of 2-methylisoborneol and geosmin in powdered activated carbon.

    PubMed

    Matsui, Yoshihiko; Sakamoto, Asuka; Nakao, Soichi; Taniguchi, Takuma; Matsushita, Taku; Shirasaki, Nobutaka; Sakamoto, Naoya; Yurimoto, Hisayoshi

    2014-09-16

    Decreasing the particle size of powdered activated carbon may enhance its equilibrium adsorption capacity for small molecules and micropollutants, such as 2-methylisoborneol (MIB) and geosmin, as well as for macromolecules and natural organic matter. Shell adsorption, in which adsorbates do not completely penetrate the adsorbent but instead preferentially adsorb near the outer surface of the adsorbent, may explain this enhancement in equilibrium adsorption capacity. Here, we used isotope microscopy and deuterium-doped MIB and geosmin to directly visualize the solid-phase adsorbate concentration profiles of MIB and geosmin in carbon particles. The deuterium/hydrogen ratio, which we used as an index of the solid-phase concentration of MIB and geosmin, was higher in the shell region than in the inner region of carbon particles. Solid-phase concentrations of MIB and geosmin obtained from the deuterium/hydrogen ratio roughly agreed with those predicted by shell adsorption model analyses of isotherm data. The direct visualization of the localization of micropollutant adsorbates in activated carbon particles provided direct evidence of shell adsorption.

  6. Compact hydrogen/helium isotope mass spectrometer

    DOEpatents

    Funsten, Herbert O.; McComas, David J.; Scime, Earl E.

    1996-01-01

    The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently, no fieldable D or molecular speciation detectors exist. Furthermore, the present spectrometer has a significant advantage over traditional T detectors: no confusion of the measurements by other beta-emitters, and complete separation of atomic and molecular species of equivalent atomic mass (e.g., HD and .sup.3 He).

  7. Zinc isotope fractionation during surface adsorption by bacteria

    NASA Astrophysics Data System (ADS)

    Kafantaris, F. A.; Borrok, D. M.

    2011-12-01

    The cycling and transport of zinc (Zn) in natural waters is partly controlled by its adsorption and uptake by bacterial communities. These reactions are reflected in changes in the ratios of stable Zn isotopes; however, the magnitudes and directions of these changes are largely unconstrained. In the current work, we attempt to define Zn isotope fractionation factors for bacteria-Zn interactions by performing adsorption experiments with representative Gram-positive (Bacillus subtilis) and Gram-negative (Pseudomonas mendocina) bacteria. Experiments included, (1) pH-dependent adsorption using differing bacteria:Zn ratios, (2) Zn loading at constant pH, and (3) kinetics and reversibility experiments. Results indicate that Zn adsorption is fully reversible for both bacterial species. Moreover, under the same experimental conditions both bacterial species adsorbed Zn to similar extents. Initial isotopic analysis (using a Nu Instruments MC-ICP-MS) demonstrates that, as the extent of adsorption increases, the heavier Zn isotopes are preferentially incorporated as bacterial-surface complexes. Under conditions of low bacteria:Zn ratio, the Δ66Znbacteria-solution was about 0.3% for both bacterial species. This separation factor is similar to that found in other studies involving the complexation of Zn with biologic or organic components. For example, the complexation of Zn with Purified Humic Acid (PHA) resulted in a Δ66ZnPHA-solution of +0.24% [1], and sorption of Zn onto two separate diatom species resulted in Δ66Znsolid-solution of +0.43% and +0.27%, respectively [2]. These results suggest that Zn complexation with functional groups common to bacteria and natural organic matter may be a process that universally incorporates the heavier Zn isotopes. Our current work is focused on quantifying Zn isotope fractionation during metabolic incorporation by separating this effect from surface adsorption reactions. [1] Jouvin et al., (2009) Environ. Sci. Technol., 43(15) 5747

  8. Hydrogen Adsorption in Zeolite Studied with Sievert and Thermogravimetric Methods

    NASA Astrophysics Data System (ADS)

    Lesnicenoks, P.; Sivars, A.; Grinberga, L.; Kleperis, J.

    2012-08-01

    Natural clinoptilolite (mixture from clinoptilolite, quartz and muscovite) is activated with palladium and tested for hydrogen adsorption capability at temperatures RT - 200°C. Thermogravimetric and volumetric methods showed that zeolite activated with palladium (1.25%wt) shows markedly high hydrogen adsorption capacity - up to 3 wt%. Lower amount of adsorbed hydrogen (~1.5 wt%) was found for raw zeolite and activated with higher amount of palladium sample. Hypothesis is proposed that the heating of zeolite in argon atmosphere forms and activates the pore structure in zeolite material, where hydrogen encapsulation (trapping) is believed to occur when cooling down to room temperature. An effect of catalyst (Pd) on hydrogen sorption capability is explained by spillover phenomena were less-porous fractions of natural clinoptilolite sample (quartz and muscovite) are involved.

  9. Enthalpy and entropy effects in hydrogen adsorption on carbon nanotubes.

    PubMed

    Efremenko, Irena; Sheintuch, Moshe

    2005-07-05

    Interaction energies and entropies associated with hydrogen adsorption on the inner and outer surfaces of zigzag single-wall carbon nanotubes (SWCNT) of various diameters are analyzed by means of molecular mechanics, density functional theory, and ab initio calculations. For a single molecule the strongest interaction, which is 3.5 greater than that with the planar graphite sheet, is found inside a (8,0) nanotube. Adsorption on the outer surfaces is weaker than that on graphite. Due to the steric considerations, both processes are accompanied by an extremely strong decline in entropy. Absence of specific adsorption sites and weak attractive interaction between hydrogen molecules within carbon nanotubes results in their close packing at low temperatures. Using the calculated geometric and thermodynamic parameters in Langmuir isotherms we predict the adsorption capacity of SWCNTs at room temperature to be smaller than 1 wt % even at 100 bar.

  10. Temperature-dependent adsorption of hydrogen, deuterium, and neon on porous Vycor glass

    NASA Astrophysics Data System (ADS)

    Huber, T. E.; Scardino, D.; Tsou, H. L.

    1995-10-01

    Adsorption isotherms of H2, D2, and Ne have been measured in the temperature range from 15 K to the corresponding critical points in samples of porous Vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. A model-independent approach allows us to fit the data for coverages ranging from submonolayer to thin film, below capillary condensation, for each adsorbate at all temperatures with a temperature-independent curve. This characteristic curve represents the distribution of adsorption sites versus the adsorption potential. In the intermediate coverage range, the isotherms exhibit the modified Frenkel-Halsey-Hill (FHH) behavior. The adsorption saturates for low-adsorption potentials. The characteristic curve is a useful universal curve since it is roughly the same for the three species investigated. We examine the relative strengths of the surface potentials and densities of the two isotopic modifications of hydrogen and of the more classical Ne adsorbed on porous Vycor glass. The characteristic adsorption curve is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces which places importance on the porosity of the surface, and Halsey's model, which is an extension of the FHH isotherm that takes into account the long-range variations of substrate adsorption potential.

  11. Tritium Isotope Separation Using Adsorption-Distillation Column

    SciTech Connect

    Fukada, Satoshi

    2005-07-15

    In order to miniaturize the height of a distillation tower for the detritiation of waste water from fusion reactors, two experiments were conducted: (1) liquid frontal chromatography of tritium water eluting through an adsorption column and (2) water distillation using a column packed with adsorbent particles. The height of the distillation tower depends on the height equivalent to a theoretical plate, HETP, and the equilibrium isotope separation factor, {alpha}{sub H-T}{sup equi}. The adsorption action improved not only HETP but also {alpha}{sub H-T}{sup equi}. Since the adsorption-distillation method proposed here can shorten the tower height with keeping advantages of the distillation, it may bring an excellent way for miniaturizing the distillation tower to detritiate a large amount of waste water from fusion reactors.

  12. Hydrogen isotope separation using molecular sieve of synthetic zeolite 3A

    SciTech Connect

    Kotoh, K.; Kimura, K.; Nakamura, Y.; Kudo, K.

    2008-07-15

    It is known that hydrogen isotope molecules can be adsorbed easily onto synthetic zeolite 4A, 5A, and 13X at the liquid-nitrogen temperature of 77.4 K. We show here that hydrogen and deuterium are not adsorptive onto zeolite 3A at the same temperature. This phenomenon is explained by assuming the molecular sieve function in zeolite-3A-crystalline lattice structure. From a series of pseudo-isobaric experiments, it is also shown that the sieving phenomenon appears in a range above 77.4 K. This behavior is interpreted as resulting on the dependence of sieve's mesh size on temperature, where the sieving effect is considered to appear at a certain temperature. In this interpretation, an isotopic difference between hydrogen and deuterium is suggested to exist in the sieving effect appearance temperatures. This is endorsed in the result of pseudo-isobaric experiments. This temperature deference is very significant because that indicates the possibility of an effective method of hydrogen isotope separation. This possibility is verified through an experimental series of adsorption-desorption with a mixture of H{sub 2} and D{sub 2}, where the gas samples adsorbed through the sieve operated at intentionally selected temperatures are isolated and then analyzed. The result demonstrates remarkable values of isotope separation factor. (authors)

  13. Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

    USGS Publications Warehouse

    Coplen, T.B.; Hanshaw, B.B.

    1973-01-01

    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

  14. Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

    NASA Astrophysics Data System (ADS)

    Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

    2008-02-01

    Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10

  15. Quantum-chemistry calculations of hydrogen adsorption in MOF-5.

    PubMed

    Gomez, Diego A; Combariza, Aldo F; Sastre, German

    2009-10-28

    High concentrations of molecular hydrogen adsorption on MOF-5 were evaluated at the semiempirical PM6 (periodic and cluster) and ab initio MP2 (cluster) theoretical levels. From the semiempirical calculations, an uptake of 3.9% weight on the inorganic building unit of MOF-5 was estimated, in good agreement with a recent accurate estimation of 4.5-5.2%. Although PM6 allows a correct estimation of the maximum uptake, the adsorption energy was overestimated and hence ab initio calculations, including a correlation treatment at the MP2 level as well as corrections for basis set superposition error, were performed with full optimisation, including the 6-31G basis set, which rendered an adsorption energy (per hydrogen molecule) of -0.14 kcal mol(-1). The crucial role of the quality of the basis set, as well as the importance of simulating high hydrogen loading (resembling experimental measurements), are remarked. Single point calculations (using the 6-31G geometry) with improved basis sets 6-31G(d,p) and 6-31++G(d,p) yielded adsorption energies of -0.33 and -0.57 kcal mol(-1), the latter in reasonable agreement with a recent experimental estimation of -1.0 kcal mol(-1). The role of the intermolecular hydrogen interactions is highlighted in this study, since many previous computational studies were performed at low hydrogen loadings, far from the experimental uptake conditions.

  16. Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

    SciTech Connect

    Matsuyama, M.; Kondo, M.; Noda, N.; Tanaka, M.; Nishimura, K.

    2015-03-15

    In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

  17. Investigation of Hydrogen Adsorption on Single Wall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Nam, Sang-Hun; Jeong, Seong Hun; Lee, Soon-Bo; Boo, Jin-Hyo

    We have investigated adsorption and desorption condition of atomic hydrogen on single-walled nanotubes (SWCNTs) using ultraviolet photoelectron spectroscopy (UPS) and thermal desorption spectroscopy (TDS). The SWCNTs were made by the high pressure carbon monoxide (HiPCO) method. In our results, we observe from UPS data absorptive states reduce with increasing hydrogen doses and a new peak is developed near 8.6 eV and other points. But this peak is gradually diminished with pumping time. The TDS data show two characteristic peaks at 640 and 790K. By comparing with density functional calculations, we propose these peaks to be related to the presence of atomic hydrogen. Therefore, we can know that there are two adsorption sites on SWCNTs. Also we observed physisorption and chemisorption site by pumping time. We note that the UPS data are fully recoverable after hydrogen desorption at 1200K.

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

    PubMed

    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.

  19. Adsorption process to recover hydrogen from feed gas mixtures having low hydrogen concentration

    DOEpatents

    Golden, Timothy Christopher; Weist, Jr., Edward Landis; Hufton, Jeffrey Raymond; Novosat, Paul Anthony

    2010-04-13

    A process for selectively separating hydrogen from at least one more strongly adsorbable component in a plurality of adsorption beds to produce a hydrogen-rich product gas from a low hydrogen concentration feed with a high recovery rate. Each of the plurality of adsorption beds subjected to a repetitive cycle. The process comprises an adsorption step for producing the hydrogen-rich product from a feed gas mixture comprising 5% to 50% hydrogen, at least two pressure equalization by void space gas withdrawal steps, a provide purge step resulting in a first pressure decrease, a blowdown step resulting in a second pressure decrease, a purge step, at least two pressure equalization by void space gas introduction steps, and a repressurization step. The second pressure decrease is at least 2 times greater than the first pressure decrease.

  20. Equations of state and phase diagrams of hydrogen isotopes

    SciTech Connect

    Urlin, V. D.

    2013-11-15

    A new form of the semiempirical equation of state proposed for the liquid phase of hydrogen isotopes is based on the assumption that its structure is formed by cells some of which contain hydrogen molecules and others contain hydrogen atoms. The values of parameters in the equations of state of the solid (molecular and atomic) phases as well as of the liquid phase of hydrogen isotopes (protium and deuterium) are determined. Phase diagrams, shock adiabats, isentropes, isotherms, and the electrical conductivity of compressed hydrogen are calculated. Comparison of the results of calculations with available experimental data in a wide pressure range demonstrates satisfactory coincidence.

  1. Cadmium isotope fractionation during adsorption to Mn-oxyhydroxide

    NASA Astrophysics Data System (ADS)

    Wasylenki, L. E.; Swihart, J. W.

    2013-12-01

    The heavy metal cadmium is of interest both as a toxic contaminant in groundwater and as a critical nutrient for some marine diatoms [1], yet little is known about the biogeochemistry of this element. Horner et al. [2] suggested that Cd stable isotopes could potentially enable reconstruction of biological use of Cd in the marine realm: since cultured diatoms fractionate Cd isotopes [3], and ferromanganese crusts appear to incorporate a faithful record of deepwater Cd isotopes [2], depth profiles in such crusts may yield information about the extent of Cd assimilation of isotopically light Cd by diatoms over time. Although no work has yet been published regarding the use of stable isotopes to track reactive transport of Cd in contaminated aquifers, others have recently demonstrated the potential of isotopes to track reactions affecting the mobility of other toxic metals (e.g., [4]). With both of these potential applications in mind, we conducted two sets of experiments, at low and high ionic strength, in which Cd partially adsorbed to potassium birnessite. Our goals are to quantify the fractionations and to constrain the mechanisms governing Cd isotope behavior during adsorption to an environmentally abundant scavenger of Cd. Suspensions of synthetic birnessite were doped with various amounts of dissolved Cd2+ at pH ~8.3. Following reaction, the dissolved and adsorbed pools of Cd were separated by filtration, purified by anion exchange chromatography, and analyzed by multicollector ICP-MS using a double-spike routine. In all cases, lighter isotopes preferentially adsorbed to the birnessite particles. At low ionic strength (I<0.01m), we observed a small fractionation of 0.15‰×0.05 (Δ114/112) that was constant as a function of the fraction of Cd adsorbed. This indicates a small equilibrium isotope effect, likely driven by a subtle shift in coordination geometry for Cd during adsorption. In a groundwater system with continuous flow of dissolved Cd, this

  2. Adsorption of hydrogen and porous structure of active carbons

    SciTech Connect

    Gavrilov, V. Yu.

    1995-09-01

    Adsorption of hydrogen on active carbons is investigated at 77.4 K. The main features of the comparative method are described for treating the sorption isotherms obtained for the solids with a well developed surface in super micropores and mesopores.

  3. Hydrogen isotope systematics of submarine basalts

    USGS Publications Warehouse

    Kyser, T.K.; O'Neil, J.R.

    1984-01-01

    The D/H ratios and water contents in fresh submarine basalts from the Mid-Atlantic Ridge, the East Pacific Rise, and Hawaii indicate that the primary D/H ratios of many submarine lavas have been altered by processes including (1) outgassing, (2) addition of seawater at magmatic temperature, and (3) low-temperature hydration of glass. Decreases in ??D and H2O+ from exteriors to interiors of pillows are explained by outgassing of water whereas inverse relations between ??D and H2O+ in basalts from the Galapagos Rise and the FAMOUS Area are attributed to outgassing of CH4 and H2. A good correlation between ??D values and H2O is observed in a suite of submarine tholeiites dredged from the Kilauea East Rift Zone where seawater (added directly to the magma), affected only the isotopic compositions of hydrogen and argon. Analyses of some glassy rims indicate that the outer millimeter of the glass can undergo lowtemperature hydration by hydroxyl groups having ??D values as low as -100. ??D values vary with H2O contents of subaerial transitional basalts from Molokai, Hawaii, and subaerial alkali basalts from the Society Islands, indicating that the primary ??D values were similar to those of submarine lavas. Extrapolations to possible unaltered ??D values and H2O contents indicate that the primary ??D values of most thoteiite and alkali basalts are near -80 ?? 5: the weight percentages of water are variable, 0.15-0.35 for MOR tholeiites, about 0.25 for Hawaiian tholeiites, and up to 1.1 for alkali basalts. The primary ??D values of -80 for most basalts are comparable to those measured for deep-seated phlogopites. These results indicate that hydrogen, in marked contrast to other elements such as Sr, Nd, Pb, and O, has a uniform isotopic composition in the mantle. This uniformity is best explained by the presence of a homogeneous reservoir of hydrogen that has existed in the mantle since the very early history of the Earth. ?? 1984.

  4. Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

    NASA Technical Reports Server (NTRS)

    Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

    1983-01-01

    In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

  5. Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

    NASA Technical Reports Server (NTRS)

    Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

    1983-01-01

    In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

  6. Preparation of narrow pores carbon suitable for hydrogen sulfide adsorption

    SciTech Connect

    Tanada, S.; Kita, T.; Boki, K.; Kozaki, Y.

    1985-01-01

    Microporous N-containing activated carbon (N-CAC) suitable for hydrogen sulfide adsorption was prepared by impregnating raw activated carbon with a 25% methylol melamine urea solution and then heating it at different temperatures from 100 to 1000/sup 0/C. The structures of raw activated carbon and N-CAC No. 8 carbonized at the most suitable temperature 850/sup 0/C have been discussed based on applying the Dubinin-Radushkevich equation to adsorption isotherm of hydrogen sulfide. The 12.2% increase in micropore volume of N-CAC No.8 result from the numerical increase of micropores rather than radial expansion of micropores. The relation of q and ..delta..S could be consistently explained by the interaction of hydrogen sulfide with micropores of adsorbents.

  7. Isotopic tracing of hydrogen transport and trapping in nuclear materials.

    PubMed

    Chêne, Jacques; Martin, Frantz

    2017-07-28

    Some illustrations of the use of deuterium or tritium for isotopic tracing of hydrogen absorption, transport and trapping in nuclear materials are presented. Isotopic tracing of hydrogen has been shown to be successful for the determination of the boundaries conditions for hydrogen desorption or absorption in a material exposed to a hydrogen source. Also, the unique capabilities of isotopic tracing and related techniques to characterize H interactions with point defects and dislocations acting as moving traps has been demonstrated. Such transport mechanisms are considered to play a major role in some stress corrosion cracking and hydrogen embrittlement mechanisms.This article is part of the themed issue 'The challenges of hydrogen and metals'. © 2017 The Author(s).

  8. Hydrogen isotope type-curves of very hot crude oils.

    PubMed

    Fekete, József; Sajgó, Csanád; Demény, Attila

    2011-01-15

    Several crude oil accumulations in the Pannonian Basin are trapped in uncommonly hot (>170°C) reservoirs. Their maturities range from mature to very mature on the basis of cracking parameters of their biological marker homologous series (ratio of products to reactants). A stable carbon isotopic study of these oils, poor in biological markers commonly used for correlation purposes, did not provide a reliable oil-to-oil correlation. As an alternative tool, the hydrogen isotope compositions of oil fractions separated on the basis of different polarities were measured, and hydrogen isotope type-curves were generated for a set of mature to very mature crude oil samples. This method of presenting hydrogen isotope composition of fractions as type-curves is novel. Nineteen samples (17 crude oils from SE-Hungary, 1 oil condensate and 1 artificial oil) were chosen for the present study. The aim was to examine the applicability of hydrogen isotope type-curves in oil-to-oil correlation and to test the simultaneous application of carbon and hydrogen isotope type-curves in the field of petroleum geochemistry. We have shown that, although the conventionally used co-variation plots proved to be inadequate for the correlation of these hot and mature oils, the simultaneous use of carbon and the newly introduced hydrogen isotope type-curves allows us to group and distinguish oils of different origins.

  9. Cd Isotope Fractionation During Adsorption Varies with Salinity

    NASA Astrophysics Data System (ADS)

    Wasylenki, L. E.; Montanez, G.; Anbar, A. D.

    2009-12-01

    Because its marine concentration profile is very similar to that of phosphate [1], Cd is considered to have potential as a paleophosphate or paleonutrient proxy in the geologic record. Previous work [2,3] has established that lighter isotopes of Cd are preferentially assimilated by phytoplankton, leaving surface waters isotopically heavy. Another recent study [4] suggests that analysis of Cd isotope variations in transects of ferromanganese crusts could reveal past variations in the extent to which Cd, and thus phosphate, has been depleted over time. This idea presumes that the extent of consumption of Cd by phytoplankton is reflected in the isotopic composition of seawater and that the Cd isotopic composition of seawater is in turn faithfully recorded in ferromanganese crusts. To test the latter assumption, Rehkämper et al. [4] measured the Cd isotopic composition of 15 Fe-Mn crusts from various ocean basins and found that 13 of those samples were within analytical error of the Cd isotopic composition of deep seawater from [3], indicating that Cd often does not fractionate appreciably during incorporation into ferromanganese crusts. Other studies [5,6] have likewise revealed little or no variation in Cd isotopic compositions among various terrestrial rocks and carbonaceous chondrites, suggesting that few earth processes significantly fractionate Cd isotopes. To test this conclusion experimentally, we performed adsorption experiments in which aqueous Cd was allowed to adsorb to synthetic birnessite (Mn oxyhydroxide). Stock solutions of dissolved Cd and birnessite suspension were mixed and agitated from 1 to 48 hours at room temperature. Some experiments had 0.1m KNO3 as background electrolyte, while others had 0.3m NaCl + 0.1m KNO3. After filtration, both the fluid with remaining dissolved Cd and solids with adsorbed Cd were purified with anion exchange chemistry. Column yields and proportions of dissolved and adsorbed Cd were determined by ICP-MS, and isotope

  10. A superior process for forming titanium hydrogen isotopic films

    NASA Technical Reports Server (NTRS)

    Steinberg, R.; Alger, D. L.; Cooper, D. W.

    1975-01-01

    Process forms stoichiometric, continuous, strongly bonded titanium hydrogen isotopic films. Films have thermal and electrical conductivities approximately the same as bulk pure titanium, ten times greater than those of usual thin films.

  11. Thermodynamics of hydrogen adsorption on metal-organic frameworks.

    PubMed

    Areán, Carlos O; Chavan, Sachin; Cabello, Carlos P; Garrone, Edoardo; Palomino, Gemma T

    2010-10-25

    Interaction between adsorbed hydrogen and the coordinatively unsaturated Mg(2+) and Co(2+) cationic centres in Mg-MOF-74 and Co-MOF-74, respectively, was studied by means of variable-temperature infrared (VTIR) spectroscopy. Perturbation of the H(2) molecule by the cationic adsorbing centre renders the H--H stretching mode IR-active at 4088 and 4043 cm(-1) for Mg-MOF-74 and Co-MOF-74, respectively. Simultaneous measurement of integrated IR absorbance and hydrogen equilibrium pressure for spectra taken over the temperature range of 79-95 K allowed standard adsorption enthalpy and entropy to be determined. Mg-MOF-74 showed ΔH(0)=-9.4 kJ mol(-1) and ΔS(0)=-120 J mol(-1) K(-1), whereas for Co-MOF-74 the corresponding values of ΔH(0)=-11.2 kJ mol(-1) and ΔS(0)=-130 J mol(-1) K(-1) were obtained. The observed positive correlation between standard adsorption enthalpy and entropy is discussed in the broader context of corresponding data for hydrogen adsorption on cation-exchanged zeolites, with a focus on the resulting implications for hydrogen storage and delivering.

  12. Longitudinal dispersion coefficient depending on superficial velocity of hydrogen isotopes flowing in column packed with zeolite pellets at 77.4 K

    SciTech Connect

    Kotoh, K.; Kubo, K.; Takashima, S.; Moriyama, S.T.; Tanaka, M.; Sugiyama, T.

    2015-03-15

    Authors have been developing a cryogenic pressure swing adsorption system for hydrogen isotope separation. In the problem of its design and operation, it is necessary to predict the concentration profiles developing in packed beds of adsorbent pellets. The profiling is affected by the longitudinal dispersion of gas flowing in packed beds, in addition to the mass transfer resistance in porous media of adsorbent pellets. In this work, an equation is derived for estimating the packed-bed dispersion coefficient of hydrogen isotopes, by analyzing the breakthrough curves of trace D{sub 2} or HD replacing H{sub 2} adsorbed in synthetic zeolite particles packed columns at the liquefied nitrogen temperature 77.4 K. Since specialized for hydrogen isotopes, this equation can be considered to estimate the dispersion coefficients more reliable for the cryogenic hydrogen isotope adsorption process, than the existing equations. (authors)

  13. On Hydrogen and Helium embrittlement in Isotopic tailoring Experiments

    SciTech Connect

    Gelles, David S.; Hamilton, Margaret L.; Oliver, Brian M.; Greenwood, Lawrence R.

    2000-09-01

    The results of shear punch testing performed on irradiated isotopically tailored alloys are considered in terms of hydrogen and helium embrittlement in order to quantify the observed behavior. The results indicate that hydrogen embrittlement may be more significant than helium embrittlement.

  14. Adsorption of hydrogen on stable and metastable Ir(100) surfaces

    NASA Astrophysics Data System (ADS)

    Arman, Mohammad Alif; Klein, Andreas; Ferstl, Pascal; Valookaran, Abhilash; Gustafson, Johan; Schulte, Karina; Lundgren, Edvin; Heinz, Klaus; Schneider, Alexander; Mittendorfer, Florian; Hammer, Lutz; Knudsen, Jan

    2017-02-01

    Using the combination of high resolution core level spectroscopy and density functional theory we present a detailed spectroscopic study for all clean and hydrogen covered phases of Ir(100). The results are complemented by an investigation of the hydrogen desorption process from various phases using temperature programmed desorption spectroscopy and scanning tunneling microscopy. In total, all experimentally determined core level shifts match very well with those predicted by density functional theory based on established structural models. In particular, we find for the (bridge site) adsorption on the unreconstructed 1×1 phase that the initial core level shift of surface Ir atoms is altered by +0.17 eV for each Ir-H bond formed. In the submonolayer regime we find evidence for island formation at low temperatures. For the H-induced deconstructed 5×1-H phase we identify four different surface core level shifts with two of them being degenerate. Finally, for the reconstructed 5×1-hex phase also four surface components are identified, which undergo a rather rigid core level shift of +0.15 eV upon hydrogen adsorption suggesting a similarly homogeneous charge transfer to all Ir surface atoms. Thermodesorption experiments for the 5×1-H phase reveal two different binding states for hydrogen independent of the total coverage. We conclude that the surface always separates into patches of fully covered deconstructed and uncovered reconstructed phases. We could also show by tunneling microscopy that with the desorption of the last hydrogen atom from the deconstructed unit cell the surface instantaneously reverts into the reconstructed state. Eventually, we could determine the saturation coverage upon molecular adsorption for all phases to be θmax1 × 1 - H = 1.0 ML , θmax5 × 1 - H = 0.8 ML , and θmax5 × 1 - hex - H ≥ 1.0 ML .

  15. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    SciTech Connect

    Aldridge, F.T.

    1984-05-09

    A study was made of the properties of metal hydrides which may be suitable for use in chromatographic separation of hydrogen isotopes. Sixty-five alloys were measured, with the best having a hydrogen-deuterium separation factor of 1.35 at 60/sup 0/C. Chromatographic columns using these alloys produced deuterium enrichments of up to 3.6 in a single pass, using natural abundance hydrogen as starting material. 25 references, 16 figures, 4 tables.

  16. Experimental stand for studies of hydrogen isotopes permeation

    SciTech Connect

    Brad, S.; Stefanescu, I.; Stefan, L.; Lazar, A.; Vijulie, M.; Sofilca, N.; Bornea, A.; Vasut, F.; Zamfirache, M.; Bidica, N.; Postolache, C.; Matei, L.

    2008-07-15

    As a result of the high probability of hydrogen isotope permeation through materials used in high-temperature reactor operations, the interaction of hydrogen isotopes with metallic structural materials proposed to be used for fusion reactor designing is of great importance for safety considerations. Determining the parameters of the interaction between hydrogen isotopes and different materials, is therefore essential to accurately calculate recycling, outgassing, loading, permeation and hydrogen embrittlement. The permeation tests were made in collaboration with IFIN Bucuresti inside of a special glove-box to avail their radioactive protection expertise. This investigation programme is ongoing. In this paper we describe the permeation stand facility and the preliminary tests carried out to date. (authors)

  17. Investigation of Morphology and Hydrogen Adsorption Capacity of Disordered Carbons

    NASA Astrophysics Data System (ADS)

    He, Lilin; Melnichenko, Yuri; Gallego, Nidia; Contescu, Cristian

    2014-03-01

    We have applied small angle neutron scattering (SANS) technique to study the morphologies and hydrogen adsorption capabilities of wood-based ultramicroporous carbon and poly(furfuryl alcohol) derived carbon. The Polydispersed Spherical model and chord length analysis of the scattering profiles were performed to obtain morphological parameters such as average pore size and pore size distribution of the dry carbons, which agreed reasonably well with the independent gas sorption measurements. The hydrogen physisorbed in these two carbons at room temperature and moderate pressures was investigated by In-situ SANS measurements. The experimental data analyzed using a modified Kalliat model for decoupling scattering contributions from pores with different sizes indicates that the molecular hydrogen condenses preferentially in narrow micropores at all measured pressures, which supports the theoretical prediction by quantum mechanical and thermodynamical models.

  18. Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

    DOEpatents

    Tanaka, John; Reilly, Jr., James J.

    1978-01-01

    This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

  19. Carbon and Hydrogen Isotopic Fractionation during Anaerobic Biodegradation of Benzene

    PubMed Central

    Mancini, Silvia A.; Ulrich, Ania C.; Lacrampe-Couloume, Georges; Sleep, Brent; Edwards, Elizabeth A.; Sherwood Lollar, Barbara

    2003-01-01

    Compound-specific isotope analysis has the potential to distinguish physical from biological attenuation processes in the subsurface. In this study, carbon and hydrogen isotopic fractionation effects during biodegradation of benzene under anaerobic conditions with different terminal-electron-accepting processes are reported for the first time. Different enrichment factors (ɛ) for carbon (range of −1.9 to −3.6‰) and hydrogen (range of −29 to −79‰) fractionation were observed during biodegradation of benzene under nitrate-reducing, sulfate-reducing, and methanogenic conditions. These differences are not related to differences in initial biomass or in rates of biodegradation. Carbon isotopic enrichment factors for anaerobic benzene biodegradation in this study are comparable to those previously published for aerobic benzene biodegradation. In contrast, hydrogen enrichment factors determined for anaerobic benzene biodegradation are significantly larger than those previously published for benzene biodegradation under aerobic conditions. A fundamental difference in the previously proposed initial step of aerobic versus proposed anaerobic biodegradation pathways may account for these differences in hydrogen isotopic fractionation. Potentially, C-H bond breakage in the initial step of the anaerobic benzene biodegradation pathway may account for the large fractionation observed compared to that in aerobic benzene biodegradation. Despite some differences in reported enrichment factors between cultures with different terminal-electron-accepting processes, carbon and hydrogen isotope analysis has the potential to provide direct evidence of anaerobic biodegradation of benzene in the field. PMID:12513995

  20. Hydrogen adsorption in thin films of Prussian blue analogue

    SciTech Connect

    Yang, Dali; Ding, Vivian; Luo, Junhua; Currier, Robert P; Obrey, Steve; Zhao, Yusheng

    2008-01-01

    Quartz crystal microbalance with dissipation (QCM-D) measurement was used to investigate the kinetics of the molecular hydrogen adsorption into thin films of prussian blue analogues - Cu{sub 3}[Co(CN){sub 6}]{sub 2} at ambient conditions. Although the equilibrium adsorption seems to be independent of the thickness, the adsorption rate substantially decreases with the thickness of the films. In addition, the reversibility of H{sub 2} adsorption into the Cu{sub 3}[Co(CN){sub 6}]{sub 2} films was investigated. The results indicate that the Cu{sub 3}[Co(CN){sub 6}]{sub 2} maily interacts with H{sub 2} molecules physically. The highest H{sub 2} uptake by the Cu{sub 3}[Co(CN){sub 6}]{sub 2} films is obtained when the gas phase is stagnant inside the testing cell. However, the unusual high H{sub 2} uptake obtained from the QCM-D measurement makes us question how reliable this analytic methodology is.

  1. Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

    PubMed Central

    Weinrauch, I.; Savchenko, I.; Denysenko, D.; Souliou, S. M.; Kim, H-H; Le Tacon, M.; Daemen, L. L.; Cheng, Y.; Mavrandonakis, A.; Ramirez-Cuesta, A. J.; Volkmer, D.; Schütz, G.; Hirscher, M.; Heine, T.

    2017-01-01

    The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol−1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gas phase. Large difference in adsorption enthalpy of 2.5 kJ mol−1 between D2 and H2 results in D2-over-H2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H2/D2 mixtures allows the prediction of selectivities for tritium-containing isotopologues. PMID:28262794

  2. Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

    NASA Astrophysics Data System (ADS)

    Weinrauch, I.; Savchenko, I.; Denysenko, D.; Souliou, S. M.; Kim, H.-H.; Le Tacon, M.; Daemen, L. L.; Cheng, Y.; Mavrandonakis, A.; Ramirez-Cuesta, A. J.; Volkmer, D.; Schütz, G.; Hirscher, M.; Heine, T.

    2017-03-01

    The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol-1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gas phase. Large difference in adsorption enthalpy of 2.5 kJ mol-1 between D2 and H2 results in D2-over-H2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H2/D2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.

  3. Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

    DOE PAGES

    Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.; ...

    2017-03-06

    The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol-1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gas phase.more » Large difference in adsorption enthalpy of 2.5 kJ mol-1 between D2 and H2 results in D2-over-H2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H2/D2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

  4. Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites.

    PubMed

    Weinrauch, I; Savchenko, I; Denysenko, D; Souliou, S M; Kim, H-H; Le Tacon, M; Daemen, L L; Cheng, Y; Mavrandonakis, A; Ramirez-Cuesta, A J; Volkmer, D; Schütz, G; Hirscher, M; Heine, T

    2017-03-06

    The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol(-1)) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gas phase. Large difference in adsorption enthalpy of 2.5 kJ mol(-1) between D2 and H2 results in D2-over-H2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H2/D2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.

  5. Evaluation of the isosteric heat of adsorption at zero coverage for hydrogen on activated carbons

    NASA Astrophysics Data System (ADS)

    Dohnke, E.; Beckner, M.; Romanos, J.; Olsen, R.; Wexler, C.; Pfeifer, P.

    2011-03-01

    Activated carbons made from corn cob show promise as materials for high-capacity hydrogen storage. As part of our characterization of these materials, we are interested in learning how different production methods affect the adsorption energies. In this talk, we will show how hydrogen adsorption isotherms may be used to calculate these adsorption energies at zero coverage using Henry's law. We will additionally discuss differences between the binding energy and the isosteric heat of adsorption by applying this analysis at different temperatures.

  6. Effect of metal adatoms on hydrogen adsorption properties of phosphorene

    NASA Astrophysics Data System (ADS)

    Yu, Zhiyuan; Lei, Shuangying; Wan, Neng; Luan, Shan; Shen, Haiyun; Yu, Hong

    2017-04-01

    Based on first-principles density functional theory, we have investigated hydrogen storage on metal adatoms decorated phosphorene. Almost all metals including alkali, alkaline, 3d, 4d and 5d transition metals (TM) as well as post-TMs are considered to decorate phosphorene, and most metals exhibit an enhancement of H2 adsorption energy (E a), except for Zn, Cd, Hg, and all post-TMs. Nine metals show ideal Ea within the energy window 0.2-0.6 eV/H2 for practical application purposes. Among them, Li, Sc, Ti, Y, Zr, and La exhibit superior adsorption abilities of 3-5 H2 per adatom. Based on local density of states and Barder analyses, underlying mechanisms of interaction between phosphorene, metal, and H2 are also discussed.

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

    NASA Astrophysics Data System (ADS)

    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

  8. Hydrogen isotope separation in carbon nanotubes: calculation of coupled rotational and translational States at high densities.

    PubMed

    Garberoglio, Giovanni; Johnson, J Karl

    2010-03-23

    The effect of the quantized rotational degrees of freedom of hydrogen on the adsorption and sieving properties in carbon nanotubes is studied using computer simulations. We have developed a highly efficient multiple timestep algorithm for hybrid Monte Carlo sampling of quantized rotor configurations and extended the grand canonical Boltzmann bias method to rigid linear molecules. These new computational tools allow us to calculate accurately the quantum sieving selectivities for cases of extreme two-dimensional confinement as a function of pressure. The para-T2/para-H2 selectivity at 20 K is analyzed as a function of the tube diameter and the density of adsorbed hydrogen. Extraordinarily high selectivities, up to 2.6 x 10(8), are observed in the narrowest nanotube. The quantized nature of the rotational degrees of freedom is found to dramatically affect adsorption and selectivity for hydrogen isotopes adsorbed in very narrow nanotubes. The T2/H2 zero-pressure selectivity increases from 2.4 x 10(4) to 1.7 x 10(8) in the (3,6) nanotube at 20 K when quantum rotations are accounted for. The isotopic selectivity is found to increase with pressure, tending to a constant value at saturation. A simplified mean-field model is used to discuss the origin of this behavior.

  9. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    NASA Technical Reports Server (NTRS)

    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.

  10. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    USGS Publications Warehouse

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

    2011-01-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  11. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    NASA Astrophysics Data System (ADS)

    Ni, Yunyan; Ma, Qisheng; Ellis, Geoffrey S.; Dai, Jinxing; Katz, Barry; Zhang, Shuichang; Tang, Yongchun

    2011-05-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

  12. Local doping of graphene devices by selective hydrogen adsorption

    SciTech Connect

    Park, Min; Park, Yung Woo E-mail: kbh37@incheon.ac.kr; Yun, Yong Ju; Jun, Yongseok; Lee, Minwoo; Jeong, Dae Hong; Kim, Byung Hoon E-mail: kbh37@incheon.ac.kr

    2015-01-15

    N-type graphene fabricated by exposure to hydrogen gas has been previously studied. Based on this property of graphene, herein, we demonstrate local doping in single-layer graphene using selective adsorption of dissociative hydrogen at 350 K. A graphene field effect transistor was produced covered with PMMA on half of the graphene region. The charge neutrality point of the PMMA-window region shifted to a negative gate voltage (V{sub G}) region prominently compared with that of the PMMA-covered region. Consequently, a single graphene p-n junction was obtained by measuring the V{sub G}-dependent resistance of the whole graphene region. This method presents opportunities for developing and controlling the electronic structure of graphene and device applications.

  13. Thermal effects in dynamic storage of hydrogen by adsorption

    SciTech Connect

    Lamari, M.; Aoufi, A.; Malbrunot, P.

    2000-03-01

    Thermal effects in dynamic hydrogen storage by adsorption at room temperature and high pressure are studied theoretically and experimentally. The system of adsorbate-adsorbent used was hydrogen in granular activated carbon. The theoretical analysis was based on heat- and mass-transfer modeling in a packed-bed adsorber, with particular emphasis on the thermal effects occurring during charge and discharge steps. The influence of gas flow rate and storage pressure (up to 15 MPa) on the total amount stored or delivered was investigated. Operating conditions were compatible with practical application for onboard vehicle storage. The experimental study was carried out in cylindrical 2-L reservoirs filled with granular activated carbon in which the bed temperature was measured at various positions. The temperature changes during both charge and discharge agreed well with the model predictions.

  14. Hydrogen recycle and isotope exchange from dense carbon films

    SciTech Connect

    Clausing, R.E.; Heatherly, L.

    1987-03-01

    Dense carbon films were prepared by deposition from hydrogen plasmas to which methane was added. The initial hydrogen recycle coefficient from the films ranges from more than two to less than one. The films contain large amounts of hydrogen (up to 50 at. %). They adjust themselves to provide recycling coefficients near unity. Isotope changeover times tend to be long. The reservoir of hydrogen instantly available to the plasma to maintain or stabilize the recycle coefficient and isotopic composition of the plasma is 10/sup 15/ cm/sup -2/ or greater depending on film preparation, temperature, and prior plasma exposure conditions. Simulator observations tend to support and improve the understanding of the observations in TEXTOR and JET; however, they also point out the need for control of film deposition and operating parameters to provide desirable and reproducible properties. The films and the hydrogen isotopes they contain can be removed easily by plasma processes. Since the hydrogen in these films is relatively immobile except in the zone reached by energetic particles, or at temperatures above 400/sup 0/C, dense carbon films may be useful in managing the tritium recovery from near-term fusion experiments.

  15. Isosteric heat of hydrogen adsorption on MOFs: comparison between adsorption calorimetry, sorption isosteric method, and analytical models

    NASA Astrophysics Data System (ADS)

    Kloutse, A. F.; Zacharia, R.; Cossement, D.; Chahine, R.; Balderas-Xicohténcatl, R.; Oh, H.; Streppel, B.; Schlichtenmayer, M.; Hirscher, M.

    2015-12-01

    Isosteric heat of adsorption is an important parameter required to describe the thermal performance of adsorptive storage systems. It is most frequently calculated from adsorption isotherms measured over wide ranges of pressure and temperature, using the so-called adsorption isosteric method. Direct quantitative estimation of isosteric heats on the other hand is possible using the coupled calorimetric-volumetric method, which involves simultaneous measurement of heat and adsorption. In this work, we compare the isosteric heats of hydrogen adsorption on microporous materials measured by both methods. Furthermore, the experimental data are compared with the isosteric heats obtained using the modified Dubinin-Astakhov, Tóth, and Unilan adsorption analytical models to establish the reliability and limitations of simpler methods and assumptions. To this end, we measure the hydrogen isosteric heats on five prototypical metal-organic frameworks: MOF-5, Cu-BTC, Fe-BTC, MIL-53, and MOF-177 using both experimental methods. For all MOFs, we find a very good agreement between the isosteric heats measured using the calorimetric and isosteric methods throughout the range of loading studied. Models' prediction on the other hand deviates from both experiments depending on the MOF studied and the range of loading. Under low-loadings of less than 5 mol kg-1, the isosteric heat of hydrogen adsorption decreases in the order Cu-BTC > MIL-53 > MOF-5 > Fe-BTC > MOF-177. The order of isosteric heats is coherent with the strength of hydrogen interaction revealed from previous thermal desorption spectroscopy measurements.

  16. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds

    NASA Astrophysics Data System (ADS)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular

  17. RECTIFIED ABSORPTION METHOD FOR THE SEPARATION OF HYDROGEN ISOTOPES

    DOEpatents

    Hunt, C.D.; Hanson, D.N.

    1961-10-17

    A method is described for separating and recovering heavy hydrogen isotopes from gaseous mixtures by multiple stage cyclic absorption and rectification from an approximate solvent. In particular, it is useful for recovering such isoteoes from ammonia feedstock streams containing nitrogen solvent. Modifications of the process ranging from isobaric to isothermal are provided. Certain impurities are tolerated, giving advantages over conventional fractional distillation processes. (AEC)

  18. A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

    USDA-ARS?s Scientific Manuscript database

    Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

  19. Hydrogen Isotopic Systematics of Nominally Anhydrous Phases in Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Tucker, Kera

    Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the mantle) is less so. In fact, the hydrogen isotope composition of the primordial martian mantle is of great interest since it has implications for the origin and abundance of water on that planet. Martian meteorites could provide key constraints in this regard, since they crystallized from melts originating from the martian mantle and contain phases that potentially record the evolution of the H 2O content and isotopic composition of the interior of the planet over time. Examined here are the hydrogen isotopic compositions of Nominally Anhydrous Phases (NAPs) in eight martian meteorites (five shergottites and three nakhlites) using Secondary Ion Mass Spectrometry (SIMS). This study presents a total of 113 individual analyses of H2O contents and hydrogen isotopic compositions of NAPs in the shergottites Zagami, Los Angeles, QUE 94201, SaU 005, and Tissint, and the nakhlites Nakhla, Lafayette, and Yamato 000593. The hydrogen isotopic variation between and within meteorites may be due to one or more processes including: interaction with the martian atmosphere, magmatic degassing, subsolidus alteration (including shock), and/or terrestrial contamination. Taking into consideration the effects of these processes, the hydrogen isotope composition of the martian mantle may be similar to that of the Earth. Additionally, this study calculated upper limits on the H2O contents of the shergottite and nakhlite parent melts based on the measured minimum H2O abundances in their maskelynites and pyroxenes, respectively. These calculations, along with some petrogenetic assumptions based on previous studies, were subsequently used

  20. Isotopic composition of atmospheric hydrogen and methane

    USGS Publications Warehouse

    Bainbridge, A.E.; Suess, H.E.; Friedman, I.

    1961-01-01

    IN a recent communication, Bishop and Taylor1 express the opinion that the tritium concentration of free hydrogen in the atmosphere has been rising over the past ten years, with a doubling time of approximately 18 months. The authors suspect that artificial tritium was released into the atmosphere several years before the Castle test series in 1954, which is commonly assumed to have led to the first pronounced rise in the tritium concentration of terrestrial surface water. Bishop and Taylor's communication includes a diagram of the logarithms of all the experimentally determined tritium values in free atmospheric hydrogen plotted against time. The plot shows that the values follow a straight line that includes the first value obtained by Faltings and Harteck2 on atmospheric hydrogen collected in 1948. ?? 1961 Nature Publishing Group.

  1. Lignin methoxyl hydrogen isotope ratios in a coastal ecosystem

    NASA Astrophysics Data System (ADS)

    Feakins, Sarah J.; Ellsworth, Patricia V.; Sternberg, Leonel da Silveira Lobo

    2013-11-01

    Stable hydrogen isotope ratios of plant lignin methoxyl groups have recently been shown to record the hydrogen isotopic composition of meteoric water. Here we extend this technique towards tracing water source variations across a saltwater to freshwater gradient in a coastal, subtropical forest ecosystem. We measure the hydrogen isotopic composition of xylem water (δDxw) and methoxyl hydrogen (δDmethoxyl) to calculate fractionations for coastal mangrove, buttonwood and hammock tree species in Sugarloaf Key, as well as buttonwoods from Miami, both in Florida, USA. Prior studies of the isotopic composition of cellulose and plant leaf waxes in coastal ecosystems have yielded only a weak correlation to source waters, attributed to leaf water effects. Here we find δDmethoxyl values range from -230‰ to -130‰, across a 40‰ range in δDxw with a regression equation of δDmethoxyl ‰ = 1.8 * δDxw - 178‰ (R2 = 0.48, p < 0.0001, n = 74). This is comparable within error to the earlier published relationship for terrestrial trees which was defined across a much larger 125‰ isotopic range in precipitation. Analytical precision for measurements of δD values of pure CH3I by gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is σ = 6‰ (n = 31), which is considerably better than for CH3I liberated through cleavage with HI from lignin with σ = 18‰ (n = 26). Our results establish that δDmethoxyl can record water sources and salinity incursion in coastal ecosystems, where variations sufficiently exceed method uncertainties (i.e., applications with δD excursions >50‰). For the first time, we also report yields of propyl iodide, which may indicate lignin synthesis of propoxyl groups under salt-stress.

  2. Controlling the spin of co atoms on pt(111) by hydrogen adsorption.

    PubMed

    Dubout, Q; Donati, F; Wäckerlin, C; Calleja, F; Etzkorn, M; Lehnert, A; Claude, L; Gambardella, P; Brune, H

    2015-03-13

    We investigate the effect of H adsorption on the magnetic properties of individual Co atoms on Pt(111) with scanning tunneling microscopy. For pristine Co atoms, we detect no inelastic features in the tunnel spectra. Conversely, CoH and CoH2 show a number of low-energy vibrational features in their differential conductance identified by isotope substitution. Only the fcc-adsorbed species present conductance steps of magnetic origin, with a field splitting identifying their effective spin as Seff=2 for CoH and 3/2 for CoH2. The exposure to H2 and desorption through tunnel electrons allow the reversible control of the spin in half-integer steps. Because of the presence of the surface, the hydrogen-induced spin increase is opposite to the spin sequence of CoHn molecules in the gas phase.

  3. Hydrogen isotope MicroChemLab FY15.

    SciTech Connect

    Robinson, David; Luo, Weifang; Stewart, Kenneth D.

    2015-09-01

    We have developed a new method to measure the composition of gaseous mixtures of any two hydrogen isotopes, as well as an inert gas component. When tritium is one of those hydrogen isotopes, there is usually some helium present, because the tritium decays to form helium at a rate of about 1% every 2 months. The usual way of measuring composition of these mixtures involves mass spectrometry, which involves bulky, energy-intensive, expensive instruments, including vacuum pumps that can quite undesirably disperse tritium. Our approach uses calorimetry of a small quantity of hydrogen-absorbing material to determine gas composition without consuming or dispersing the analytes. Our work was a proof of principle using a rather large and slow benchtop calorimeter. Incorporation of microfabricated calorimeters, such as those that have been developed in Sandia’s MicroChemLab program or that are now commercially available, would allow for faster measurements and a smaller instrument footprint.

  4. Uranium Isotopic Fractionation Induced by U(VI) Adsorption onto Common Aquifer Minerals.

    PubMed

    Jemison, N E; Johnson, T M; Shiel, A E; Lundstrom, C C

    2016-11-15

    Uranium groundwater contamination due to U mining and processing affects numerous sites globally. Bioreduction of soluble, mobile U(VI) to U(IV)-bearing solids is potentially a very effective remediation strategy. Uranium isotopes ((238)U/(235)U) have been utilized to track the progress of microbial reduction, with laboratory and field studies finding a ∼1‰ isotopic fractionation, with the U(IV) product enriched in (238)U. However, the isotopic fractionation produced by adsorption may complicate the use of (238)U/(235)U to trace microbial reduction. A previous study found that adsorption of U(VI) onto Mn oxides produced a -0.2‰ fractionation with the adsorbed U(VI) depleted in (238)U. In this study, adsorption to quartz, goethite, birnessite, illite, and aquifer sediments induced an average isotopic fractionation of -0.15‰ with the adsorbed U(VI) isotopically lighter than coexisting aqueous U(VI). In bicarbonate-bearing matrices, the fractionation depended little on the nature of the sorbent, with only birnessite producing an atypically large fractionation. In the case of solutions with ionic strengths much lower than those of typical groundwater, less isotopic fractionation was produced than U(VI) solutions with greater ionic strength. Studies using U isotope data to assess U(VI) reduction must consider adsorption as a lesser, but significant isotope fractionation process.

  5. Kinetics of hydrogen adsorption on MgH{sub 2}/CNT composite

    SciTech Connect

    Rather, Sami ullah Taimoor, Aqeel Ahmad; Muhammad, Ayyaz; Alhamed, Yahia Abobakor; Zaman, Sharif Fakhruz; Ali, Arshid Mahmood

    2016-05-15

    Highlights: • Hydrogen adsorption comparisons of commercial, milled, and MgH{sub 2} composite. • Hydrogen adsorption capacity and kinetics improves tremendously by CNT embedding. • Unsteady state modeling and simulation of adsorption kinetics. - Abstract: Magnesium hydride (MgH{sub 2})–carbon nanotubes (CNT) composite has been prepared by high-energy ball milling method and their experimental and kinetic hydrogen adsorption studies was assessed. Hydrogen adsorption studies were performed by Sievert’s volumetric apparatus and kinetic evaluation was conducted by surface chemistry and Langmuir–Hinshelwood–Hougen–Watson (LHHW) type mode. Powder X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) were performed. Hydrogen adsorption capacity of commercial MgH{sub 2}, milled MgH{sub 2}, and MgH{sub 2}/CNT composite are found to be 0.04, 0.057, and 0.059 g (H{sub 2})/g (MgH{sub 2}) at 673 K and hydrogen pressure of 4.6 MPa. Addition of 5 wt% of CNTs to MgH{sub 2} proved to be very critical to enhance hydrogen adsorption as well as to improve its kinetics. It was observed that hydrogen adsorption is not in quasi-state equilibrium and is modeled using kinetic rate laws.

  6. Molecular dynamics simulations on hydrogen adsorption in finite single walled carbon nanotube bundles.

    PubMed

    Knippenberg, M Todd; Stuart, Steven J; Cheng, Hansong

    2008-05-01

    Molecular dynamics simulations of the adsorption of hydrogen molecules in finite single-walled carbon nanotube bundles are presented using a curvature dependent force field. The heat of formation and the effective adsorption capacity are expressed as a function of H(2) distance from adsorbent. The heat of adsorption decreases rapidly with the distance and increasing H(2) loading results in weakening adsorption strength. The effects of nanotube packing and bundle thickness on hydrogen adsorption strength were investigated and the results show that the heat of adsorption can be improved slightly if hydrogen molecules are placed in thicker and inhomogeneously packed nanotube bundles. Only very small diameter nanotube bundles were found to hold promise for significant hydrogen storage for onboard applications.

  7. Poisoning effect on solubility of hydrogen isotopes in getter materials

    NASA Astrophysics Data System (ADS)

    Yamanaka, Shinsuke; Sato, Yuichi; Ogawa, Hidenori; Shirasu, Yoshirou; Miyake, Masanobu

    1991-03-01

    Hydrogen and deuterium solubilities in Ti-C and Zr-N alloys with various compositions have been measured at pressures below 100 Pa. All of the solubility data were found to follow Sieverts' law. The presence of carbon in Ti increased the solubilities of hydrogen isotopes and reduced the enthalpies of solution. The solubility increased and the enthalpy of solution decreased with addition of nitrogen into Zr. The hydrogen solubility in Ti-C and Zr-N alloys was larger than the deuterium solubility. Partial thermodynamic functions of hydrogen and deuterium in Ti-C and Zr-N alloys were obtained by a dilute solution model and compared with those in Ti-(O, N) and Zr-O alloys. The isotope effect of hydrogen and deuterium solubilities in the Ti-(O, N, C) and Zr-(O, N) alloys was discussed, and the tritium solubility in Ti-C and Zr-N alloys was evaluated from hydrogen and deuterium data.

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

    DOEpatents

    Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

    1980-01-01

    Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

  9. Molecular simulation of adsorption and diffusion of hydrogen in metal-organic frameworks.

    PubMed

    Yang, Qingyuan; Zhong, Chongli

    2005-06-23

    Metal-organic frameworks (MOFs) are thought to be a set of promising hydrogen storage materials; however, little is known about the interactions between hydrogen molecules and pore walls as well as the diffusivities of hydrogen in MOFs. In this work, we performed a systematic molecular simulation study on the adsorption and diffusion of hydrogen in MOFs to provide insight into molecular-level details of the underlying mechanisms. This work shows that metal-oxygen clusters are preferential adsorption sites for hydrogen in MOFs, and the effect of the organic linkers becomes evident with increasing pressure. The hydrogen storage capacity of MOFs is similar to carbon nanotubes, which is higher than zeolites. Diffusion of hydrogen in MOFs is an activated process that is similar to diffusion in zeolites. The information derived in this work is useful to guide the future rational design and synthesis of tailored MOF materials with improved hydrogen adsorption capability.

  10. Bandgap opening in graphene induced by patterned hydrogen adsorption.

    PubMed

    Balog, Richard; Jørgensen, Bjarke; Nilsson, Louis; Andersen, Mie; Rienks, Emile; Bianchi, Marco; Fanetti, Mattia; Laegsgaard, Erik; Baraldi, Alessandro; Lizzit, Silvano; Sljivancanin, Zeljko; Besenbacher, Flemming; Hammer, Bjørk; Pedersen, Thomas G; Hofmann, Philip; Hornekaer, Liv

    2010-04-01

    Graphene, a single layer of graphite, has recently attracted considerable attention owing to its remarkable electronic and structural properties and its possible applications in many emerging areas such as graphene-based electronic devices. The charge carriers in graphene behave like massless Dirac fermions, and graphene shows ballistic charge transport, turning it into an ideal material for circuit fabrication. However, graphene lacks a bandgap around the Fermi level, which is the defining concept for semiconductor materials and essential for controlling the conductivity by electronic means. Theory predicts that a tunable bandgap may be engineered by periodic modulations of the graphene lattice, but experimental evidence for this is so far lacking. Here, we demonstrate the existence of a bandgap opening in graphene, induced by the patterned adsorption of atomic hydrogen onto the Moiré superlattice positions of graphene grown on an Ir(111) substrate.

  11. Ab initio study of hydrogen adsorption in MOF-5.

    PubMed

    Sillar, Kaido; Hofmann, Alexander; Sauer, Joachim

    2009-03-25

    Metal-organic frameworks (MOFs) are promising adsorbents for hydrogen storage. Density functional theory and second-order Møller-Plesset perturbation theory (MP2) are used to calculate the interaction energies between H(2) and individual structural elements of the MOF-5 framework. The strongest interaction, DeltaH(77) = -7.1 kJ/mol, is found for the alpha-site of the OZn(4)(O(2)Ph)(6) nodes. We show that dispersion interactions and zero-point vibrational energies must be taken into account. Comparison of calculations done under periodic boundary conditions for the complete structure with those done for finite models cut from the MOF-5 framework shows that the interactions with H(2) originate mainly from the local environment around the adsorption site. When used within a Multi-Langmuir model, the MP2 results reproduce measured adsorption isotherms (the predicted amount is 6 wt % at 77 K and 40 bar) if we assume that the H(2) molecules preserve their rotational degrees of freedom in the adsorbed state. This allows to discriminate between different isotherms measured for different MOF-5 samples and to reliably predict isotherms for new MOF structures.

  12. Hydrogen isotope exchange in a metal hydride tube

    SciTech Connect

    Robinson, David B.

    2014-09-01

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

  13. Exploiting Diffusion Barrier and Chemical Affinity of Metal-Organic Frameworks for Efficient Hydrogen Isotope Separation.

    PubMed

    Kim, Jin Yeong; Balderas-Xicohténcatl, Rafael; Zhang, Linda; Kang, Sung Gu; Hirscher, Michael; Oh, Hyunchul; Moon, Hoi Ri

    2017-09-29

    Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ∼26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D2 through direct selective separation studies using 1:1 D2/H2 mixtures.

  14. Process for hydrogen isotope concentration between liquid water and hydrogen gas

    DOEpatents

    Stevens, William H.

    1976-09-21

    A process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas, wherein liquid water and hydrogen gas are contacted, in an exchange section, with one another and with at least one catalyst body comprising at least one metal selected from Group VIII of the Periodic Table and preferably a support therefor, the catalyst body has a liquid-water-repellent, gas permeable polymer or organic resin coating, preferably a fluorinated olefin polymer or silicone coating, so that the isotope concentration takes place by two simultaneously occurring steps, namely, ##EQU1## WHILE THE HYDROGEN GAS FED TO THE EXCHANGE SECTION IS DERIVED IN A REACTOR VESSEL FROM LIQUID WATER THAT HAS PASSED THROUGH THE EXCHANGE SECTION.

  15. Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

    USGS Publications Warehouse

    Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

    2015-01-01

    Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN

  16. Adsorption properties of polyvinyl-alcohol-grafted particles toward genistein driven by hydrogen-bond interaction.

    PubMed

    Zhang, Yanyan; Gao, Baojiao; Xu, Zeqing

    2013-05-09

    The adsorption properties of polyvinyl alcohol (PVA)-grafted silica gel particles PVA/SiO2 toward genistein are researched in this paper. The effects of the main factors on the adsorption properties are investigated, the adsorption mechanism is explored in depth, and the adsorption thermodynamics is researched. The experimental results show that the conventional hydrogen bond is formed between the hydroxyl groups with high density on the surfaces of PVA/SiO2 and the phenolic hydroxyl groups in genistein, while π-type hydrogen bond is formed between the hydroxyl groups of PVA/SiO2 and the conjugated aromatic rings. It is the two types of hydrogen bond that make the functional composite particles PVA/SiO2 produce very strong physical adsorption toward genistein. The competitive adsorption of the solvent can have severe negative impact on the adsorption capacity of genistein. Increasing temperature will weaken the hydrogen-bond interaction between PVA/SiO2 particles and genistein. The existence of electrolytes in the protic solvent will affect the adsorption negatively. The adsorption process of PVA/SiO2 particles toward genistein is exothermic and driven by enthalpy. The adsorption isotherm data matches the Langmuir model.

  17. Direct measurement of hydrogen adsorption in carbon nanotubes/nanofibers by elastic recoil detection

    NASA Astrophysics Data System (ADS)

    Naab, F. U.; Dhoubhadel, M.; Gilbert, J. R.; Gilbert, M. C.; Savage, L. K.; Holland, O. W.; Duggan, J. L.; McDaniel, F. D.

    2006-07-01

    Physi- or chemi-sorption of hydrogen in solid materials offers a viable medium for hydrogen storage since the concentration of hydrogen can exceed that in its gaseous form at high compression. Due to their unique architecture, carbon nanotubes are potentially an excellent carbon-based adsorbent for hydrogen. In this work, we report direct measurements of hydrogen adsorption using elastic recoil detection analysis in single-walled, double-walled, and multi-walled nanotubes, as well as carbon nanofibers. Results are presented for hydrogen adsorption treatment at ambient temperature and above, where chemical rather than physical adsorption is anticipated. The results show that the concentration of hydrogen in all samples over the range of conditions investigated is below 1 wt.%, which is well below that required for a viable storage media.

  18. Adsorption of hydrogen on Pt(111) and Pt(100) surfaces and its role in the HOR.

    SciTech Connect

    Strmcnik, D.; Tripkovic, D.; van der Vliet, D.; Stamenkovic, V.; Markovic, N. M.; Materials Science Division

    2008-10-01

    Hydrogen adsorption isotherms, evaluated by combination of cyclic voltammetry and chronoamperometry, are reported on Pt(1 1 1) and Pt(1 0 0) surfaces in 0.1 M HClO{sub 4}. We found that at E > 0.05 V Pt(1 1 1) and Pt(1 0 0) are only partially covered by the adsorbed hydrogen (H{sub ad}). On both surfaces, a full monolayer of the adsorbed hydrogen is completed at -0.1 V, i.e. the adsorption of atomic hydrogen is observed in the hydrogen evolution potential region. We also found, that the activity of the hydrogen oxidation reaction is mirrored by the shape of the hydrogen adsorption isotherms, implying that H{sub ad} is in fact a spectator in the HOR.

  19. Uranium Isotopic Fractionation Induced by U(VI) Adsorption Onto Common Aquifer Minerals

    NASA Astrophysics Data System (ADS)

    Jemison, N.; Johnson, T. M.; Shiel, A. E.; Lundstrom, C.

    2014-12-01

    Mining and processing of uranium (U) ore for nuclear energy and weapons has led to U contamination of groundwater. Reduction of soluble, mobile U(VI) to UO2 decreases uranium groundwater concentrations and is an important driver of natural and stimulated attenuation. 238U/235U measurements can be used to monitor and perhaps quantify U(VI) reduction; biological reduction of U(VI) has been shown to produce a ~1.0‰ isotopic fractionation in both laboratory and field settings, with the reduced product enriched in 238U. However, adsorption of U(VI) onto minerals may complicate the use of 238U/235U in this application; adsorption of U(VI) onto Mn oxides induces an isotopic fractionation of 0.2‰ with the sorbed U(VI) depleted in 238U. At present, the isotopic shift produced by adsorption of U(VI) onto other minerals has not yet been explored. This study measures U isotopic fractionation during adsorption onto goethite, birnessite, quartz, illite, and complex aquifer materials. In addition, the effect of U speciation on fractionation is also examined by adsorption of uranyl (UO22+), uranyl carbonato (such as UO2(CO3)22- and UO2(CO3)34-), and calcium uranyl carbonato (Ca2UO2(CO3)3(aq) and CaUO2(CO3)32-) ions to goethite and birnessite. Experiments are carried out with a multi-stage, batch approach, in which a U(VI)-bearing solution is exposed to three stages of adsorption, and the final solution is analyzed by a double-spike MC-ICP-MS method. This increases our ability to resolve among sorbents the extent of fractionation. Early results suggest that uranium adsorption to different minerals produces different isotopic fractionations, with quartz producing little to no fractionation (<0 .05‰), while goethite produces a 0.16‰ isotopic shift (adsorbed U(VI) depleted in 238U).

  20. Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water

    SciTech Connect

    Butler, J.P.

    1980-04-01

    The discovery, at Chalk River Nuclear Laboratories, of a simple method of wetproofing platinum catalysts so that they retain their activity in liquid water stimulated a concentrated research program for the development of catalysts for the hydrogen-water isotopic exchange reaction. This paper reviews 10 years of study which have resulted in the development of highly active platinum catalysts which remain effective in water for periods greater than a year. The most efficient way to use these catalysts for the separation of hydrogen isotopes is in a trickle bed reactor which effects a continuous separation. The catalyst is packed in a column with hydrogen and water flowing countercurrently through the bed. The overall isotope transfer rate measured for the exchange reaction is influenced by various parameters, such as hydrogen and water flow rates, temperature, hydrogen pressure, and platinum metal loading. The effect of these parameters as well as the improved performance obtained by diluting the hydrophobic catalyst with inert hydrophilic packing are discussed. The hydrophobic catalysts can be effectively used in a variety of applications of particular interest in the nuclear industry. A Combined Electrolysis Catalytic Exchange - Heavy Water Process (CECE-HWP) is being developed at Chalk River with the ultimate aim of producing parasitic heavy water from electrolytic hydrogen streams. Other more immediate applications include the final enrichment of heavy water and the extraction of tritium from light and heavy water. Pilot plant studies on these latter processes are currently in progress.

  1. Hydrogen isotopes transport parameters in fusion reactor materials

    NASA Astrophysics Data System (ADS)

    Serra, E.; Benamati, G.; Ogorodnikova, O. V.

    1998-06-01

    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.

  2. Comparison of methods for separating small quantities of hydrogen isotopes from an inert gas

    SciTech Connect

    Willms, R.S.; Tuggle, D.; Birdsell, S.; Parkinson, J.; Price, B.; Lohmeir, D.

    1998-03-01

    It is frequent within tritium processing systems that a small amount of hydrogen isotopes (Q{sub 2}) must be separated from an inert gas such as He, Ar and N{sub 2}. Thus, a study of presently available technologies for effecting such a separation was performed. A base case and seven technology alternatives were identified and a simple design of each was prepared. These technologies included oxidation-adsorption-metal bed reduction, oxidation-adsorption-palladium membrane reactor, cryogenic adsorption, cryogenic trapping, cryogenic distillation, hollow fiber membranes, gettering and permeators. It was found that all but the last two methods were unattractive for recovering Q{sub 2} from N{sub 2}. Reasons for technology rejection included (1) the method unnecessarily turns the hydrogen isotopes into water, resulting in a cumbersome and more hazardous operation, (2) the method would not work without further processing, and (3) while the method would work, it would only do so in an impractical way. On the other hand, getters and permeators were found to be attractive methods for this application. Both of these methods would perform the separation in a straightforward, essentially zero-waste, single step operation. The only drawback for permeators was that limited low-partial Q{sub 2} pressure data is available. The drawbacks for getters are their susceptibility to irreversible and exothermic reaction with common species such as oxygen and water, and the lack of long-term operation of such beds. More research is envisioned for both of these methods to mature these attractive technologies.

  3. Hydrogen Isotopic Composition of Hornblendes From Active Volcanoes of Mexico

    NASA Astrophysics Data System (ADS)

    Taran, Y.; Kusakabe, M.; Valdez, G.; Mora, J. C.

    2002-12-01

    Horblendes (Hb) crystallize in water-rich magmas in magma chambers or in deeper zones. Isotopic composition of hydrogen in OH-groups of Hb represents the water isotopic composition of magmatic fluid or dissolved magmatic volatiles and therefore, is an isotopic characteristics of magmatic water. At lower vapor pressure in conduits and shallower magma chambers, Hb can decompose and loose water with significant isotopic effects. We measured hydrogen isotopic composition of hornblendes from modern lavas and pyroclastics of El Chichon, Colima and Popocatepetl volcanoes. Hornblendes from the last and previous pyroclastic flows of El Chichon are the more abundant mineral phases (after plagioclase), showing pleochroism from green to brown. They are relatively uniform in composition (close to magnesian hastingsite hornblende), without chemical variations between cores and rims. Using the Johnson and Rutherford (1989) calibration of the Al-in-hornblende geobarometer, the hornblendes show equilibrium with the melt at pressure of 4 kb that correspond to 12 km of depth. These pressure conditions likely represent the location of the magma chamber below El Chichon volcano, however, these pressure estimates need to be confirmed. The water content of all analyzed Hbs is 1.5-1.8 wt%, but may be higher due to a minor amount of impurities of pyroxenes which sometimes are difficult to separate from Hb. Hydrogen isotopic composition in 10 samples of Hb from El Chichon of different age and facies (pumice, lithic fragments in pyroclastics) was in a narrow range -40 to -37 permil V-SMOW. Such isotopic signature corresponds to so-called "andesitic" waters, i.e. waters from subduction-related magmas, The origin of these waters is suggested to be the recycled water from subducted oceanic sediments. The data for El Chichon volcano are in the range of the already known values for subduction-related magmas though the tectonic setting of El Chichon is more complicated. The measured isotopic

  4. Effect of nitrogen doping of graphene oxide on hydrogen and hydroxyl adsorption

    NASA Astrophysics Data System (ADS)

    Min, Byeong June; Jeong, Hae Kyung

    2014-05-01

    We investigate how nitrogen-doping affects the hydrogen (H) and the hydroxyl (OH) adsorption on graphene oxide (GO) and on nitrogen-doped GO (NGO) via pseudopotential plane wave density functional calculations within the local spin density approximation. We find that the nitrogendoping brings about drastic changes in the hydrogen and the hydroxyl adsorption energetics, but its effects depend sensitively on the nitrogen configuration in NGO. The H and the OH adsorption energies are comparable only for pyrrolic NGO. In GO and quarternary NGO, the H adsorption energy is greater than the OH adsorption energy while the trend is reversed in pyridinic NGO. Also, the OH adsorption process is less affected by nitrogen-doping than the H adsorption is.

  5. Installations for separation of hydrogen isotopes by the method of chemical isotopic exchange in the `water-hydrogen` system

    SciTech Connect

    Andreev, B.M.; Sakharovsky, Y.A.; Rozenkevich, M.B.; Magomedbekov, E.P.; Park, Y.S.; Uborskiy, V.V.; Trenin, V.D.; Alekseev, I.A.; Fedorchenko, O.A.; Karpov, S.P.; Konoplev, K.A.

    1995-10-01

    The paper presents the results of more than a year of running a pilot setup for separation of hydrogen isotopes using catalytic isotopic exchange between hydrogen and liquid water. The setup is 5 m high, has the inner diameter of 28 mm, and is equipped with upper and lower reflux devices. The experimental values of HETP vary from 15 cm at T=333 K to 38 cm at T=293 K. The setup is capable of upgrading diluted heavy water with 85-90% deuterium content up to [D{sub 2}O] > 99.95 at.%, yielding daily 4 kg of the product. We also report on the progress in constructing a similar setup for eliminating tritium and an industrial setup, for which the one reported is a prototype. 10 refs., 1 fig., 3 tabs.

  6. First-principles investigation of vanadium isotope fractionation in solution and during adsorption

    NASA Astrophysics Data System (ADS)

    Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang

    2015-09-01

    Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ⁡α V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ⁡α V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.

  7. Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

    NASA Astrophysics Data System (ADS)

    van Zuilen, Kirsten; Müller, Thomas; Nägler, Thomas F.; Dietzel, Martin; Küsters, Tim

    2016-08-01

    Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass-dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 °C and 25 °C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in δ137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba /D134Ba =(m134 /m137) β). Values of β extracted from the transport model were in the range of 0.010-0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (α = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation processes, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.

  8. Impact of hydrogen isotope species on microinstabilities in helical plasmas

    NASA Astrophysics Data System (ADS)

    Nakata, Motoki; Nunami, Masanori; Sugama, Hideo; Watanabe, Tomo-Hiko

    2016-07-01

    The impact of isotope ion mass on ion-scale and electron-scale microinstabilities such as ion temperature gradient (ITG) mode, trapped electron mode (TEM), and electron temperature gradient (ETG) mode in helical plasmas are investigated by using gyrokinetic Vlasov simulations with a hydrogen isotope and real-mass kinetic electrons. Comprehensive scans for the equilibrium parameters and magnetic configurations clarify the transition from ITG mode to TEM instability, where a significant TEM enhancement is revealed in the case of inward-shifted plasma compared to that in the standard configuration. It is elucidated that the ion-mass dependence on the ratio of the electron-ion collision frequency to the ion transit one, i.e. {ν\\text{ei}}/{ω\\text{ti}}\\propto {{≤ft({{m}\\text{i}}/{{m}\\text{e}}\\right)}1/2} , leads to a stabilization of the TEM for heavier isotope ions. The ITG growth rate indicates a gyro-Bohm-like ion-mass dependence, where the mixing-length estimate of diffusivity yields γ /k\\bot2\\propto m\\text{i}1/2 . On the other hand, a weak isotope dependence of the ETG growth rate is identified. A collisionality scan also reveals that the TEM stabilization by the isotope ions becomes more significant for relatively higher collisionality in a banana regime.

  9. Isotope separation by photochromatography

    DOEpatents

    Suslick, K.S.

    1975-10-03

    A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

  10. Isotope separation by photochromatography

    DOEpatents

    Suslick, Kenneth S.

    1977-01-01

    An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

  11. Structure and hydrogen adsorption properties in low density nanoporous carbons from simulations

    SciTech Connect

    Peng, L.; Morris, James R

    2012-01-01

    We systematically model the hydrogen adsorption in nanoporous carbons over a wide range of carbon bulk densities (0.6 - 2.4 g/cm3) by using tight binding molecular dynamics simulations for the carbon structures and thermodynamics calculations of the hydrogen adsorption. The resulting structures are in good agreement with the experimental data of ultra-microporous carbon (UMC), a wood-based activated carbon, as indicated by comparisons of the microstructure at atomic level, pair distribution function, and pore size distribution. The hydrogen adsorption calculations in carbon structures demonstrate both a promising hydrogen storage capacity (excess uptake of 1.33 wt% at 298K and 5 MPa, for carbon structures at the lower range of densities) and a reasonable heat of adsorption (12-22 kJ/mol). This work demonstrates that increasing the heat of adsorption does not necessarily increase the hydrogen uptake. In fact, the available adsorption volume is as important as the isosteric heat of adsorption for hydrogen storage in nanoporous carbons.

  12. Unexpected hydrogen isotope variation in oceanic pelagic seabirds.

    PubMed

    Ostrom, Peggy H; Wiley, Anne E; Rossman, Sam; Stricker, Craig A; James, Helen F

    2014-08-01

    Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142‰ range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology.

  13. Unexpected hydrogen isotope variation in oceanic pelagic seabirds

    USGS Publications Warehouse

    Ostrom, Peggy H.; Wiley, Anne E.; Rossman, Sam; Stricker, Craig A.; James, Helen F.

    2014-01-01

    Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142% range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology.

  14. GCMC simulation of hydrogen adsorption in densely packed arrays of Li-doped and hydrogenated carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Mirabella, Simone; Celino, Massimo; Zollo, Giuseppe

    2013-11-01

    The upper threshold of hydrogen adsorption in Li-doped and hydrogenated carbon nanotube densely packed arrays is calculated to check the ability of such systems to fulfill the target indicated by the United States Department of Energy (DOE). To this aim, model potential parameters have been obtained by Density Functional Theory and have been used to calculate the adsorption isotherms in honeycomb arrays containing up to seven tubes by means of Grand-Canonical Monte Carlo simulations. A hybrid model has been developed involving both atomistic potentials for short-range interactions and integrated potentials for hydrogen interacting with distant tubes. In the pressure range explored, it is shown that the hydrogen adsorption performances of Li-doped carbon nanotubes arranged in close packed honeycomb arrays, while being enhanced with respect to pristine carbon nanotubes, are still well below the DOE targets.

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

    USGS Publications Warehouse

    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.

  16. Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

    NASA Astrophysics Data System (ADS)

    Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

    2017-05-01

    The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope

  17. Enhancement Effect of Lithium-Doping Functionalization on Hydrogen Adsorption in Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Xia, Liangzhi; Liu, Qing; Wang, Fengling; Li, Yupeng

    Grand canonical Monte-Carlo simulation was carried out to study the effect of linker functionalization by Li atoms. In this work, two new Li-doping structures, MOF-808-Li and MOF-808-OLi were theoretically constructed by physical modification and chemical modification, respectively. The results show that both these methods can improve the hydrogen storage performance significantly, owing to the Li atoms increasing the interaction energy between the hydrogen molecules and the Li-doped MOF-808. Furthermore, MOF-808-OLi shows higher hydrogen capacity in comparison to the H2 adsorption in the MOF-808-Li, this can be attributed to the new adsorption sites created by oxygen atom. The gravimetric adsorption capacity of MOF-808-OLi can reach 3.17wt.% at 77K and 1bar, which are significantly higher than the hydrogen adsorption in the unmodified MOF-808.

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

    NASA Technical Reports Server (NTRS)

    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.

  19. Hydrogen isotope separation by bipolar electrolysis with countercurrent electrolyte flow

    SciTech Connect

    Ramey, D.W.; Petek, M.; Taylor, R.D.; Fisher, P.W.; Kobisk, E.H.; Ramey, J.; Sampson, C.A.

    1980-04-01

    Separation of hydrogen isotopes has been successfully demonstrated using bipolar electrolysis combined with electrolyte flow countercurrent to the transport of hydrogen isotope species. Use of multibipolar electrode cells in a squared-off cascade is shown theoretically to be capable of efficient tritium separation. Experimental operation of multibipolar cells and analysis of their operation by McCabe-Thiele techniques is described. Palladium-25% silver alloy was found to be suitable as a material for bipolar electrodes permitting high hydrogen throughput with chemical and mechanical stability. Bipolar separation factors, at high current density, using NaOH (NaOD) as the electrolyte, are large (..cap alpha../sub DT/ = 2.0, ..cap alpha../sub HT/ = 11 at 90/sup 0/C). Calculated mass transfer, as determined using a squared-off cascade model, together with observed electrical power consumption suggest that about 21 percent less power will be required for bipolar electrolytic separation as compared with normal electrolysis. This estimate only represents the present level of development. Separation of tritium from light and heavy water using the bipolar electrolysis process appears to offer significant advantages as compared with direct electrolysis. The simplicity and efficiency of the multibipolar cell offer great potential for designing a very compact separation facility which, in turn, will minimize containment cost when high tritium concentrations are encountered.

  20. Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane

    SciTech Connect

    Jewett, J.R., Fluor Daniel Hanford

    1997-02-24

    Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing all hydrogen isotopes mixed with the stable helium isotopes. The application of this mass spectrometer were demonstrated by analyzing mixtures of deuterated methanes. In addition, it was employed to study the radiochemical Witzbach exchange reaction between tritium and methanes. A laser-Raman spectrometer was designed for analysis of tritium-containing gases and was built from individual components. A tritium-compatible, metal-sealed Raman cuvette having windows with good optical properties and additional means for measuring the stray light was first used successfully in this work. The Raman spectra of the hydrogen isotopes were acquired in the pure rotation mode and in the rotation-vibration mode and were used for on. The deuterated methanes were measured by Raman spectroscopy, the wavenumbers determined were assigned to the corresponding vibrations, and the wavenumbers for the rotational fine-structure were summarized in tables. The fundamental Vibrations of the deuterated methanes produced Witzbach reactions were detected and assigned. The fundamental vibrations of the molecules were obtained with Raman spectroscopy for the first time in this work. The @-Raman spectrometer assembled is well suited for the analysis of tritium- containing gases and is practical in combination with mass spectrometry using an Omegatron, for studying gases used in fusion.

  1. Inner radiation belt source of helium and heavy hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Leonov, A. A.; Galper, A. M.; Koldashov, S. V.; Mikhailov, V. V.; Casolino, M.; Picozza, P.; Sparvoli, R.

    Nuclear interactions between inner zone protons and atoms in the upper atmosphere provide the main source of energetic H and He isotopes nuclei in the radiation belt. This paper reports on the specified calculations of these isotope intensities using various inner zone proton intensity models (AP-8 and SAMPEX/PET PSB97), the atmosphere drift-averaged composition and density model MSIS-90, and cross-sections of the interaction processes from the GNASH nuclear model code. To calculate drift-averaged densities and energy losses of secondaries, the particles were tracked in the geomagnetic field (modelled through IGRF-95) by integrating numerically the equation of the motion. The calculations take into account the kinematics of nuclear interactions along the whole trajectory of trapped proton. The comparison with new data obtained from the experiments on board RESURS-04 and MITA satellites and with data from SAMPEX and CRRES satellites taken during different phases of solar activity shows that the upper atmosphere is a sufficient source for inner zone helium and heavy hydrogen isotopes. The calculation results are energy spectra and angular distributions of light nuclear isotopes in the inner radiation belt that may be used to develop helium inner radiation belt model and to evaluate their contribution to SEU (single event upset) rates.

  2. Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

    SciTech Connect

    Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina; Yong-Hyun, Kim

    2013-01-01

    It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principles total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.

  3. Hydrogen isotope alteration of normal alkanes during artificial maturation experiments

    NASA Astrophysics Data System (ADS)

    Wang, C.; Eley, Y.; Oakes, A.; Hren, M. T.

    2016-12-01

    Hydrogen isotopes of normal alkanes provide a record of past climate, hydrocarbon source and migration, and thermal history. Numerous authors have investigated the preservation potential of organic compounds during burial diagenesis and developed a range of molecular indicators of thermal maturity. A key uncertainty in application of organic biomarkers for paleoenvironmental work is how the δD values of individual molecular compounds changes during burial heating and thermal cracking. Studies suggest that n-alkanes are unlikely to exchange hydrogen at modest temperatures (below 150°C) over geologic time, however there is still debate over the potential for alteration of primary isotopic signatures due to the combined effect of exchange and cracking of more complex molecules. We conducted a suite of heating experiments in ambient air and oxygen-free systems using pure alkane mixtures and natural soil extracts to evaluate the preservation potential of the hydrogen isotopic composition of both short (nC20) carbon chain n-alkanes. Our data show that for pure mixtures, there is a positive shift in the δD of long carbon chains during heating of up to 12‰ and a negative shift in short chains of up to 28‰. Experiments with natural sediment extracts show 2H enrichment of long carbon chains during heating in both ambient air and oxygen free systems, and at temperatures below 150°C. These changes are accompanied by shifts in the carbon preference and average chain length. Experimental data show that there is potential for 2H/1H alteration of long-carbon chain normal alkanes during shallow burial, however these changes rarely exceed 10-15‰ before compounds are degraded to quantities below useful abundances for isotope measurements. A potentially significant result is that low temperature alteration of organics within sediments can shift the average chain length, particularly in the presence of oxygen. Thus, lithology and gas permeability may play an important role in

  4. Microscopic theory of hysteretic hydrogen adsorption in nanoporous materials.

    PubMed

    Kang, Joongoo; Wei, Su-Huai; Kim, Yong-Hyun

    2010-02-10

    Understanding gas adsorption confined in nanoscale pores is a fundamental issue with broad applications in catalysis and gas storage. Recently, hysteretic H(2) adsorption was observed in several nanoporous metal-organic frameworks (MOFs). Here, using first-principles calculations and simulated adsorption/desorption isotherms, we present a microscopic theory of the enhanced adsorption hysteresis of H(2) molecules using the MOF Co(1,4-benzenedipyrazolate) [Co(BDP)] as a model system. Using activated H(2) diffusion along the small-pore channels as a dominant equilibration process, we demonstrate that the system shows hysteretic H(2) adsorption under changes of external pressure. For a small increase of temperature, the pressure width of the hysteresis, as well as the adsorption/desorption pressure, dramatically increases. The sensitivity of gas adsorption to temperature changes is explained by the simple thermodynamics of the gas reservoir. Detailed analysis of transient adsorption dynamics reveals that the hysteretic H(2) adsorption is an intrinsic adsorption characteristic in the diffusion-controlled small-pore systems.

  5. First-principles study on hydrogen adsorption on nitrogen doped graphene

    NASA Astrophysics Data System (ADS)

    Muhammad, Rafique; Shuai, Yong; Tan, He-Ping

    2017-04-01

    In this paper we have investigated the adsorption of Hydrogen on Nitrogen doped graphene in detail by means of first-principles calculations. A comprehensive study is performed of the structural, electronic and optical properties of hydrogen atoms adsorbed on dopant atoms sites and on carbon atoms neighboring dopant atoms. The effect of doping has been investigated by varying the concentration of doping atoms from 3.125%(one atom of nitrogen in 32 host atoms) to 6.25% (two nitrogen atoms in 32 host atoms). Similarly the effect of adsorption has been investigated by varying the concentration of hydrogen atoms and also varying the adsorption sites. Band structure, partial density of states (PDOS) and optical properties of pure, nitrogen doped and hydrogen adsorbed graphene sheet were calculated using VASP (Vienna ab-initio Simulation Package). The calculated results for pure graphene sheet were then compared with nitrogen doped graphene and Hydrogen adsorbed graphene sheet. It is found that upon nitrogen doping the Dirac point in the graphene band structure shifts below the Fermi Energy level and energy gap appears at the high symmetric K-point. On the other hand, by adsorption of Hydrogen atom, there is further change in the band structure near the Fermi level and also the energy gap at the high symmetric K-point is increased. There is change in the dielectric function and refractive index of the graphene after H atoms adsorption on N-doped graphene. The overall absorption spectra is decreased in case of nitrogen doping and after adsorption process of Hydrogen atoms. However a significant red shift in absorption towards visible range of radiation is found to occur for hydrogen atoms adsorbed on nitrogen doped graphene sheet. The reflectivity peak of graphene increases in low energy region after H adsorption on N-doped graphene. The results can be used to tune the Fermi Energy level and to tailor the optical properties of graphene sheet in visible region.

  6. Equilibrium carbon and hydrogen isotope fractionation in iron

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2009-12-01

    Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin

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

    NASA Astrophysics Data System (ADS)

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

    1994-04-01

    Earlier bench-scale work at the Tritium Systems Test Assembly (TSTA) at Los Alamos National Laboratory examined a number of adsorbents for their suitability for separating low-concentration hydrogen (no tritium) from helium. One of the effective adsorbents was Linde 5A molecular sieve. Recently, experiments including tritium were conducted using practical-scale adsorbers. These tests used existing cryogenic molecular sieve beds (CMSB's) which each contain about 1.6 kg of Linde 5A molecular sieve. They are part of the TSTA integrated tritium processing system. Gas was fed to each CMSB at about 13 SLPM with a nominal composition of 99% He, 0.98% H2, and 0.02% HT. In all cases, for an extended period of time, the beds allowed no detectable (via Raman spectroscopy) hydrogen isotopes to escape in the bed effluent. Thereafter, the hydrogen isotopes appeared in the bed exit with a relatively sharp breakthrough curve. This work concludes that cryogenic molecular sieve adsorption is a practical and effective means of separating low-concentration hydrogen isotopes from a helium carrier.

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

    SciTech Connect

    Gayathri Devi, V.; Sircar, A.; Sarkar, B.

    2015-03-15

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

  9. Understanding hydrogen adsorption in metal-organic frameworks with open metal sites: a computational study.

    PubMed

    Yang, Qingyuan; Zhong, Chongli

    2006-01-19

    Recent experimental investigations show that the open metal sites may have a favorable impact on the hydrogen adsorption capacity of metal-organic frameworks (MOFs); however, no definite evidence has been obtained to date and little is known on the interactions between hydrogen and the pore walls of this kind of MOFs. In this work, a combined grand canonical Monte Carlo simulation and density functional theory calculation is performed on the adsorption of hydrogen in MOF-505, a recently synthesized MOF with open metal sites, to provide insight into molecular-level details of the underlying mechanisms. This work shows that metal-oxygen clusters are preferential adsorption sites for hydrogen, and the strongest adsorption of hydrogen is found in the directions of coordinatively unsaturated open metal sites, providing evidence that the open metal sites have a favorable impact on the hydrogen sorption capacity of MOFs. The storage capacity of hydrogen of MOF-505 at room temperature and moderate pressures is predicted to be low, in agreement with the outcome for hydrogen physisorption in other porous materials.

  10. Enhanced hydrogen adsorption on graphene by manganese and manganese vanadium alloy decoration.

    PubMed

    Pei, P; Whitwick, M B; Sun, W L; Quan, G; Cannon, M; Kjeang, E

    2017-03-23

    In this work, two kinds of novel manganese decorated (G + Mn) and manganese-vanadium co-decorated (G + MnV) graphene composites are synthesized by in situ wet chemical reduction, and their hydrogen storage properties and microstructures are characterized by Sievert-type adsorption apparatus, BET, SEM, TEM/STEM, EDX and EELS. Compared with pristine graphene, Mn decoration marginally increases the hydrogen adsorption capacity of graphene at room temperature and 4 MPa hydrogen pressure from 0.25 wt% to 0.36 wt%. On the other hand, the co-decoration of Mn and V increases the room temperature hydrogen storage capacity of graphene significantly to 1.81 wt% under 4 MPa hydrogen pressure, which is 1.56 wt% higher than the capacity of pristine graphene. The microstructures and valence states of the decorated Mn and Mn-V nanoparticles are investigated by TEM, EDX and EELS analyses, and strong interactions between the decorated nanoparticles and graphene are observed. Based on the results from structural analyses, potential enhancement mechanisms are suggested in terms of the catalytic effects of nanoparticles on graphene hydrogen adsorption. Given the relatively low cost of Mn and V metals compared to noble metals such as Pd, Pt and Au, these results demonstrate a low cost and effective way to significantly enhance the room temperature hydrogen adsorption properties of graphene for potential hydrogen storage applications.

  11. DFT study of adsorption and diffusion of atomic hydrogen on metal surfaces

    NASA Astrophysics Data System (ADS)

    Gómez, Elizabeth del V.; Amaya-Roncancio, Sebastián; Avalle, Lucía B.; Linares, Daniel H.; Gimenez, M. Cecilia

    2017-10-01

    An extensive study of adsorption and diffusion of hydrogen atoms on (100) surfaces of fcc Au, Cu, Ag and Pt was performed by means of DFT calculations. Bulk properties of those metals were calculated and compared with previous results. The adsorption distances and energies of the hydrogen atom on top, hollow and bridge sites of the (100) surfaces were calculated in order to elucidate preferential adsorption sites of hydrogen on each metal. All these calculations were done in conjunction with a study of charge distribution. Finally, diffusion of the H atom from the most stable adsorption site to the nearest neighbouring site was studied in order to obtain diffusion barrier and diffusion velocity values. The highest diffusion velocity was found to be v = 6.44 ×1011 s-1 for the case of Ag, whereas the lowest was v = 1.13 ×107 s-1 for Au.

  12. Uranium Isotope Fractionation during Adsorption, (Co)precipitation, and Biotic Reduction.

    PubMed

    Dang, Duc Huy; Novotnik, Breda; Wang, Wei; Georg, R Bastian; Evans, R Douglas

    2016-12-06

    Uranium contamination of surface environments is a problem associated with both U-ore extraction/processing and situations in which groundwater comes into contact with geological formations high in uranium. Apart from the environmental concerns about U contamination, its accumulation and isotope composition have been used in marine sediments as a paleoproxy of the Earth's oxygenation history. Understanding U isotope geochemistry is then essential either to develop sustainable remediation procedures as well as for use in paleotracer applications. We report on parameters controlling U immobilization and U isotope fractionation by adsorption onto Mn/Fe oxides, precipitation with phosphate, and biotic reduction. The light U isotope ((235)U) is preferentially adsorbed on Mn/Fe oxides in an oxic system. When adsorbed onto Mn/Fe oxides, dissolved organic carbon and carbonate are the most efficient ligands limiting U binding resulting in slight differences in U isotope composition (δ(238)U = 0.22 ± 0.06‰) compared to the DOC/DIC-free configuration (δ(238)U = 0.39 ± 0.04‰). Uranium precipitation with phosphate does not induce isotope fractionation. In contrast, during U biotic reduction, the heavy U isotope ((238)U) is accumulated in reduced species (δ(238)U up to -1‰). The different trends of U isotope fractionation in oxic and anoxic environments makes its isotope composition a useful tracer for both environmental and paleogeochemical applications.

  13. Oxygen and hydrogen isotope signatures of Northeast Atlantic water masses

    NASA Astrophysics Data System (ADS)

    Voelker, Antje H. L.; Colman, Albert; Olack, Gerard; Waniek, Joanna J.; Hodell, David

    2015-06-01

    Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 δ18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, δD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5‰ for δ18O and 0 to 2‰ for δD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high δ18O (0.5-1.1‰) and δD (3-6‰) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (δ18O: -0.1 to 0.5‰; δD: -1 to 4‰) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed δ18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0

  14. Direct observation of hydrogen adsorption sites and nanocage formation in metal-organic frameworks.

    PubMed

    Yildirim, T; Hartman, M R

    2005-11-18

    The hydrogen adsorption sites in MOF5 were determined using neutron powder diffraction along with first-principles calculations. The metal-oxide cluster is primarily responsible for the adsorption while the organic linker plays only a secondary role. Equally important, at low temperatures and high-concentration, molecules form unique interlinked high-symmetry nanoclusters with intermolecular distances as small as 3.0 Angstrom and H(2) uptake as high as 11 wt %. These results hold the key to optimizing metal-organic framework (MOF) materials for hydrogen storage applications and also suggest that MOFs can be used as templates to create artificial interlinked hydrogen nanocages with novel properties.

  15. Direct Observation of Hydrogen Adsorption Sites and Nanocage Formation in Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Yildirim, T.; Hartman, M. R.

    2005-11-01

    The hydrogen adsorption sites in MOF5 were determined using neutron powder diffraction along with first-principles calculations. The metal-oxide cluster is primarily responsible for the adsorption while the organic linker plays only a secondary role. Equally important, at low temperatures and high-concentration, H2 molecules form unique interlinked high-symmetry nanoclusters with intermolecular distances as small as 3.0 Å and H2 uptake as high as 11 wt %. These results hold the key to optimizing metal-organic framework (MOF) materials for hydrogen storage applications and also suggest that MOFs can be used as templates to create artificial interlinked hydrogen nanocages with novel properties.

  16. Adsorption of hydrogen chloride on microcrystalline silica. [solid rocket propellant exhaust

    NASA Technical Reports Server (NTRS)

    Kang, Y.; Wightman, J. P.

    1979-01-01

    The interaction of hydrogen chloride with quartz was studied to determine the extent to which silica can irreversibly remove hydrogen chloride from the atmosphere. Adsorption isotherms were measured at 30 C for hydrogen chloride on silica outgassed between 100 C and 400 C. Readsorption isotherms were also measured. The silica surface was characterized further by infrared spectroscopy, electron spectroscopy for chemical analysis, scanning electron microscopy, and immersional calorimetry. Ground debris samples obtained from the Kennedy Space Center, were likewise examined.

  17. Demonstration of compound-specific isotope analysis of hydrogen isotope ratios in chlorinated ethenes.

    PubMed

    Kuder, Tomasz; Philp, Paul

    2013-02-05

    High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

  18. Hydrogen-graphite interaction: Experimental evidences of an adsorption barrier

    NASA Astrophysics Data System (ADS)

    Aréou, E.; Cartry, G.; Layet, J.-M.; Angot, T.

    2011-01-01

    The interaction of H atoms having relatively low average kinetic energy (˜0.025 eV) with both perfectly clean and D-covered HOPG surfaces is investigated using high resolution electron energy loss spectroscopy. From this study we confirm, in a controlled fashion, the presence of the theoretically predicted adsorption barrier since no adsorption is detected for such H atoms on HOPG. Moreover, we demonstrate that the exposure of a D saturated HOPG surface to these H atoms results in the complete removal of adatoms, with no further adsorption despite the prediction of the adsorption barrier to vanish for H dimers in para configuration. Therefore, the recombinative abstraction mechanism which competes with the adsorption process is more efficient.

  19. Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition

    NASA Astrophysics Data System (ADS)

    Szynkiewicz, Anna; Borrok, David M.

    2016-01-01

    In order to better understand the factors influencing zinc (Zn) isotope composition in hydrological systems, we analyzed the δ66Zn of dissolved Zn in the streams and groundwater of the Upper and Middle Rio Grande watershed in Colorado and New Mexico, United States. The stream water samples have a wider variation of δ66Zn (-0.57 to + 0.41 ‰ relative to the JMC 3-0749-Lyon standard) than groundwater samples (-0.13 to + 0.12 ‰) and than samples from streams that are in close proximity to abandoned mining sites (+0.24 to + 0.40 ‰). Regional changes of bedrock geology, from primarily igneous rocks to primarily sedimentary rocks, have no resolvable effect on the δ66Zn of aqueous samples. Instead, an increase in water pH from 7.5 to 8.5 corresponds to a considerable decrease in the δ66Zn of dissolved Zn (R2 = - 0.37, p = 0.003, n = 22). Consequently, we link the observed Zn isotope variations to the process of adsorption of Zn onto suspended sediment and bedrock minerals (average Δ66Znadsorbed-dissolved = + 0.31 ‰). Our results are in good agreement with previous experimental and empirical studies suggesting that Zn adsorption leads to a residual dissolved pool enriched in light Zn isotopes. Given that anthropogenic Zn sources can also be responsible for lowering of δ66Zn, and may overlap with the pH/adsorption effect on δ66Zn, the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing Zn isotopes in this and other aquatic systems.

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

    Treesearch

    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...

  1. Shape of the hydrogen adsorption regions of MOF-5 and its impact on the hydrogen storage capacity

    NASA Astrophysics Data System (ADS)

    Cabria, I.; López, M. J.; Alonso, J. A.

    2008-11-01

    The adsorption of molecular hydrogen on a metal-organic framework (MOF) material, MOF-5, has been studied using the density-functional formalism. The calculated potential-energy surface shows that there are two main adsorption regions: both near the OZn4 oxide cores at the vertices of the cubic skeleton of MOF-5. The adsorption energies in those regions are between 100 and 130 meV/molecule. Those adsorption regions have the shape of long, wide, and deep connected trenches and passage of the molecule between regions needs to surpass small barriers of 30-50 meV. The shape of these regions, and not only the presence of metal atoms, explains the large storage capacity measured for MOF-5. The elongated shape explains why some authors have previously identified only one type of adsorption site, associated to the Zn oxide core, and others identified two or three sites. One should consider adsorption regions rather than adsorption sites. A third region of adsorption is near the benzenic rings of the MOF-5. We have also analyzed the possibility of dissociative chemisorption. The chemisorption energy with respect to two separated H atoms is 1.33 eV/H atom; but, since dissociating the free molecule costs 4.75 eV, the physisorbed H2 molecule is more stable than the dissociated chemisorbed state by about 2 eV. Dissociation of the adsorbed molecule costs less energy, but the dissociation barrier is still high.

  2. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling.

    PubMed

    Poirier, Eric; Dailly, Anne

    2009-05-20

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn4O(1,3,5-benzenetribenzoate)2, MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g(-1). An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g(-1) at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol(-1) in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn4O(1,4-benzenedicarboxylate)3, IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  3. Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling

    NASA Astrophysics Data System (ADS)

    Poirier, Eric; Dailly, Anne

    2009-05-01

    Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn4O(1,3,5-benzenetribenzoate)2, MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g-1. An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid. These liquid state properties observed under supercritical conditions reveal a remarkable effect of nanoscale confinement. The entire set of adsorption isotherms can be well described using a micropore filling model. The latter is used, in particular, to determine the absolute amounts adsorbed and the adsorption enthalpy. When expressed in terms of absolute adsorption, the isotherms show considerable hydrogen storage capacities, reaching up to 125 mg g-1 at 50 K and 25 bar. The adsorption enthalpies are calculated as a function of fractional filling and range from 3 to 5 kJ mol-1 in magnitude, in accordance with physisorption. These results are discussed with respect to a similar analysis performed on another Zn-based MOF, Zn4O(1,4-benzenedicarboxylate)3, IRMOF-1, presented recently. It is found that both materials adsorb hydrogen by similar mechanisms.

  4. A DFT study of hydrogen adsorption on Be, Mg and Ca frameworks in erionite zeolite

    NASA Astrophysics Data System (ADS)

    Fellah, Mehmet Ferdi

    2017-02-01

    The molecular hydrogen adsorption was investigated on additional frameworks with earth alkaline metal atoms (Be, Mg and Ca) in 24T ERI zeolite cluster model by means of Density Functional Theory study. HOMO and LUMO energy values, chemical potential, chemical hardness, electronegativity, adsorption energy and adsorption enthalpy values have been calculated in this study. Mg-ERI and Ca-ERI clusters have much lower chemical potentials with much lower adsorption energy values when compared to the value of Be-ERI cluster. Additionally, they are softer than Be-ERI cluster with respect to their lower chemical hardness values. Hydrogen adsorption enthalpy values were computed as -3.6 and -3.9 kJ/mol on Mg-ERI and Ca-ERI clusters, respectively. These adsorption enthalpy values are significantly larger than the enthalpy value of liquefaction for hydrogen molecule. This consequently specifies that Mg-ERI and Ca-ERI zeolite structures which have higher chemical reactivity appear to be a promising candidate cryoadsorbent for hydrogen storage.

  5. Intracrystalline site preference of hydrogen isotopes in borax

    SciTech Connect

    Pradhananga, T.M.; Matsuo, S.

    1985-01-03

    The total hydrogen involved in borax synthesized at 25/sup 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/sup 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/sub 4/O/sub 5/(OH)/sub 4/) are much more enriched in deuterium than those of the cationic group (Na/sub 2/ x 8H/sub 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/sup 0/C. At -21/sup 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.

  6. Hydrogen-Isotopic Ratios of Lipids From Hydrogen-Consuming Bacteria

    NASA Astrophysics Data System (ADS)

    Campbell, B. J.; Fox, D. N.; Sessions, A. L.; Valentine, D. L.

    2005-12-01

    Molecular hydrogen (H2) plays several key roles in aquatic sediments. Metabolized by a wide variety of prokaryotes, it both serves a vehicle for interspecies electron transfer and exerts thermodynamic control over microbial metabolic processes. H2 is typically depleted in deuterium (D) by up to 600‰ relative to water, providing a potential isotopic marker for H2-consuming organisms. Preservation of that isotopic signal in sediments requires that molecular H2 can be an indirect source of carbon-bound hydrogen in microbial lipids, a question that is the target of our ongoing laboratory-based investigations. Here we report compound-specific H-isotopic analyses of lipids extracted from H2-consuming bacteria grown under defined isotopic conditions (δD-H2 and δD-H2O). Cupriavidus necator, an aerobe, is a facultatively lithoautotrophic "knallgas" bacterium. C. necator was grown on H2 + O2 + CO2 in liquid media with differing δD-H2O values. The results of compound-specific isotopic analysis show a strong correlation between the H-isotopic ratio of lipids and that of H2O in the growth medium. Cultures grown in media of δD-H2O = -24‰ produced lipids in which δD values were from -258‰ to -197‰. In media of δD-H2O = +527‰, δD-lipid values were from +117‰ to +228‰. In media of δD-H2O = +1115‰, δD-lipid values were from +514‰ to +675‰. Linear regression was performed on the data from each lipid compound (R2 > 0.9994 in all cases). Regression lines intercepted the δD-lipid axis between -966‰ ([D]/[H] = 5.23×10-6) and -827‰ ([D]/[H] = 1.60×10-5); slopes were between and 0.670 and 0.764. These results indicate that the isotopic composition of lipids is entirely controlled by that of water, i.e. that the isotopic depletion of H2 is not recorded in the lipids - in sharp contrast to previous results from another hydrogenotroph, Sporomusa sp., where part of lipid H is derived indirectly from H2. The results are consistent with two possibilities: 1

  7. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  8. Effects of Crystallinity on Zn Isotope Fractionation during Adsorption onto Silica Surfaces

    NASA Astrophysics Data System (ADS)

    Nelson, J.; Wasylenki, L.; Bargar, J.; Brown, G. E.; Maher, K.

    2016-12-01

    Interactions between metal ions and minerals surfaces and attendant isotopic fractionation are highly dependent on mineral surface properties and the local chemical environment. Here we present equilibrium adsorption isotherms, X-ray absorption spectroscopy, and isotopic measurements to illustrate the effects of substrate crystallinity, ionic strength, and surface coverage on zinc complexation and isotope fractionation. In low ionic strength solutions (I = 0.004 M) at surface loadings <0.6 µmol m-2, zinc adsorbs to the quartz surface as an outer-sphere complex in octahedral coordination with oxygen atoms (RZn-O = 2.05 Å), with no significant isotopic fractionation from aqueous Zn. At similar chemical conditions, outer-sphere Zn adsorption complexes are not observed on amorphous silica surfaces. At higher ionic strength (I = 0.1 M) at higher surface loading (>0.6 µmol m-2), Zn forms inner-sphere, monodentate complexes in tetrahedral coordination with oxygen atoms at the quartz surface (RZn-O = 1.98 Å), with a measured equilibrium isotope fractionation of Δ66/64Znaqueous-sorbed= -0.62 ±0.05‰. At similar chemical conditions and surface loading, Zn forms inner-sphere, monodentate complexes at the amorphous silica surface, in tetrahedral coordination, with shorter zinc-oxygen bond distances (RZn-O = 1.94 Å) and a larger measured equilibrium isotope fractionation of Δ66/64Znaqueous-sorbed= -0.91 ±0.05‰. First row transition metals generally exhibit inner-sphere complexation with simple metal oxide surfaces; however, our results demonstrate that this assumption is not always supported. The impact of crystallinity on the type of adsorbed complexes formed at mineral surfaces is reflected in the equilibrium isotope fractionation. Moreover, different degrees of crystallinity alter bond distances in sorption complex geometries, which result in different equilibrium isotope fractionation factors.

  9. Hydrogen Adsorption on Activated Carbon an Carbon Nanotubes Using Volumetric Differential Pressure Technique

    NASA Astrophysics Data System (ADS)

    Sanip, S. M.; Saidin, M. A. R.; Aziz, M.; Ismail, A. F.

    2010-03-01

    A simple hydrogen adsorption measurement system utilizing the volumetri differential pressure technique has been designed, fabricated and calibrated. Hydroge adsorption measurements have been carried out at temperatures 298 K and 77 K on activate carbon and carbon nanotubes with different surface areas. The adsorption data obtained will b helpful in understanding the adsorption property of the studied carbon materials using th fundamentals of adsorption theory. The principle of the system follows the Sievert-type metho The system measures a change in pressure between the reference cell, R1 and the sample cell S1, S2, S3 over a certain temperature range. R1, S1, S2, and S3 having known fixed volume The sample temperatures will be monitored by thermocouple TC while the pressures in R1 an S1, S2, S3 will be measured using a digital pressure transducer. The maximum operatin pressure of the pressure transducer is 20 bar and calibrated with an accuracy of ±0.01 bar. Hig purity hydrogen is being used in the system and the amount of samples for the study is betwee 1.0-2.0 grams. The system was calibrated using helium gas without any samples in S1, S2 an S3. This will provide a correction factor during the adsorption process providing an adsorption free reference point when using hydrogen gas resulting in a more accurate reading of th adsorption process by eliminating the errors caused by temperature expansion effects and oth non-adsorption related phenomena. The ideal gas equation of state is applied to calculate th hydrogen adsorption capacity based on the differential pressure measurements. Activated carbo with a surface area of 644.87 m2/g showed a larger amount of adsorption as compared to multiwalled nanotubes (commercial) with a surface area of 119.68 m2/g. This study als indicated that there is a direct correlation between the amounts of hydrogen adsorbed an surface area of the carbon materials under the conditions studied and that the adsorption significant at 77

  10. First-principles study of hydrogen adsorption on Mo(1 1 0)

    NASA Astrophysics Data System (ADS)

    Zhou, Y. G.; Zu, X. T.; Nie, J. L.; Xiao, H. Y.

    2008-07-01

    First-principles calculations based on density functional theory-generalized gradient approximation method have been performed for hydrogen (H) adsorption on Mo(1 1 0) surface. For various coverages, the hollow (hol) site was found to be the most stable binding site. The adsorption energy of this site was slightly increased as the increasing of hydrogen coverage. Subsurface (sub) occupation at low and medium coverages was ruled out while it became to be stable at the coverage of 1 ML. This is also supported by the potential energy surface (PES) study for hydrogen diffusing from hol to sub site. It's interesting to find a surface reconstruction at the coverage of 1 ML, which is characterized by the lateral shift of the topmost layer for the sub adsorption. At higher coverage, the local density of states (LDOS) analysis showed that a new peak was clearly visible which was ascribed to a surface state induced by hydrogen adsorption. This surface state was mostly localized on the hydrogen atom and the first Mo layer, implying the hybridization of the hydrogen 1s states and the Mo metal states.

  11. Adsorption dynamics for the system hydrogen/palladium and its relation to the surface electronic structure

    NASA Astrophysics Data System (ADS)

    Resch, Ch.; Berger, H. F.; Rendulic, K. D.; Bertel, E.

    1994-09-01

    We have determined differential sticking coefficients for a monoenergetic nozzle beam of hydrogen on Pd(111) and Pd(110). In particular the energy dependence and the angular variation of the initial sticking coefficient were measured. The results indicate that adsorption of hydrogen on palladium occurs in parallel processes through a direct path with an activation barrier of perhaps 50 meV or less and a precursor path. There is relatively little difference in the adsorption properties of the (111) and the (110) plane. The appearance of a molecular precursor on the (111) plane can be related to the electronic structure of palladium, in particular to the absence of occupied Shockley surface states, as compared to Ni (111) and Pt (111). Pre-adsorbed potassium on a (110) plane acts as an inhibitor to adsorption. Different inhibiting mechanisms are observed for the direct adsorption path and the precursor path. At high potassium coverage the precursor path is completely suppressed.

  12. Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

    NASA Astrophysics Data System (ADS)

    Larson, T. E.

    2012-12-01

    Transport of carbon dioxide through porous media can be affected by diffusion, advection and adsorption processes. Developing new tools to understand which of these processes dominates migration of CO2 or other gases in the subsurface is important to a wide range of applications including CO2 storage. Whereas advection rates are not affected by isotope substitution in CO2, adsorption and diffusion constants are. For example, differences in the binary diffusion constant calculated between C12O2-He and C13O2-He results in a carbon isotope fractionation whereby the front of the chromatographic peak is enriched in carbon-12 and the tail of the peak is enriched in carbon-13. Interestingly, adsorption is shown to have an opposite, apparent inverse affect whereby the lighter isotopologues of CO2 are preferentially retained by the chromatographic column and the heavier isotopologues are eluted first. This apparent inverse chromatographic effect has been ascribed to Van der Waals dispersion forces. Smaller molar volumes of the heavier isotopologues resulting from increased bond strength (shorter bond length) effectively decreases Van der Waals forces in heavier isotopologues compared to lighter isotopologues. Here we discuss the possible application of stable isotope values measured across chromatographic peaks to differentiate diffusion-dominated from adsorption-dominated transport processes for CO2. Separate 1-dimensional flow-through columns were packed with quartz and illite, and one remained empty. Dry helium was used as a carrier gas. Constant flow rate, temperature and column pressure were maintained. After background CO2 concentrations were minimized and constant, a sustained pulse of CO2 was injected at the head of the column and the effluent was sampled at 4 minute intervals for CO2 concentration, and carbon and oxygen isotope ratios. The quartz-sand packed and empty columns resulted in similar trends in concentration and isotope ratios whereby CO2 concentrations

  13. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

    Wang, X.; Xu, H.; Atia-Tul-Noor, A.; Hu, B. T.; Kielpinski, D.; Sang, R. T.; Litvinyuk, I. V.

    2016-08-01

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H2/D2 gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H2 and D2 . The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  14. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption.

    PubMed

    Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao; Subbaraman, Ram; Danilovic, Nemanja; van der Vliet, Dennis; Paulikas, Arvydas P; Stamenkovic, Vojislav R; Markovic, Nenad M

    2013-04-01

    The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt₀.₁Ru₀.₉) with an optimal balance between the active sites that are required for the adsorption/dissociation of H₂ and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

  15. Stable hydrogen isotopic analysis of nanomolar molecular hydrogen by automatic multi-step gas chromatographic separation.

    PubMed

    Komatsu, Daisuke D; Tsunogai, Urumu; Kamimura, Kanae; Konno, Uta; Ishimura, Toyoho; Nakagawa, Fumiko

    2011-11-15

    We have developed a new automated analytical system that employs a continuous flow isotope ratio mass spectrometer to determine the stable hydrogen isotopic composition (δD) of nanomolar quantities of molecular hydrogen (H(2)) in an air sample. This method improves previous methods to attain simpler and lower-cost analyses, especially by avoiding the use of expensive or special devices, such as a Toepler pump, a cryogenic refrigerator, and a special evacuation system to keep the temperature of a coolant under reduced pressure. Instead, the system allows H(2) purification from the air matrix via automatic multi-step gas chromatographic separation using the coolants of both liquid nitrogen (77 K) and liquid nitrogen + ethanol (158 K) under 1 atm pressure. The analytical precision of the δD determination using the developed method was better than 4‰ for >5 nmol injections (250 mL STP for 500 ppbv air sample) and better than 15‰ for 1 nmol injections, regardless of the δD value, within 1 h for one sample analysis. Using the developed system, the δD values of H(2) can be quantified for atmospheric samples as well as samples of representative sources and sinks including those containing small quantities of H(2) , such as H(2) in soil pores or aqueous environments, for which there is currently little δD data available. As an example of such trace H(2) analyses, we report here the isotope fractionations during H(2) uptake by soils in a static chamber. The δD values of H(2) in these H(2)-depleted environments can be useful in constraining the budgets of atmospheric H(2) by applying an isotope mass balance model.

  16. Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

    PubMed Central

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

    2011-01-01

    Copper isotopes may prove to be a useful tool for investigating bacteria–metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu–bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5–6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution–solid = δ65Cusolution – δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to –0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution–solid ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is

  17. Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

    Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ 65Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive ( Bacillus subtilis) and Gram-negative ( Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ 65Cu solution-solid = δ 65Cu solution - δ 65Cu solid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to -0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ 65Cu solution-solid ranging from ˜+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is

  18. Surface morphology of orthorhombic Mo2C catalyst and high coverage hydrogen adsorption

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Tian, Xinxin; Yang, Yong; Li, Yong-Wang; Wang, Jianguo; Beller, Matthias; Jiao, Haijun

    2016-09-01

    High coverage hydrogen adsorption on twenty two terminations of orthorhombic Mo2C has been systematically studied by using density functional theory and ab initio thermodynamics. Hydrogen stable coverage on the surfaces highly depends on temperatures and H2 partial pressure. The estimated hydrogen desorption temperatures under ultra-high vacuum condition on Mo2C are in reasonable agreement with the available temperature-programmed desorption data. Obviously, hydrogen adsorption can affect the surface stability and therefore modify the surface morphology of Mo2C. Upon increasing the chemical potential of hydrogen which can be achieved by increasing the H2 partial pressure and/or decreasing the temperature, the proportions of the (001), (010), (011) and (100) surfaces increase, while those of the (101), (110) and (111) surfaces decrease. Among these surfaces, the (100) surface is most sensitive upon hydrogen adsorption and the (111) surface is most exposed under a wide range of conditions. Our study clearly reveals the role of hydrogen on the morphology of orthorhombic Mo2C catalyst in conjugation with hydro-treating activity.

  19. NMR study of hydrogen adsorption on Rh/TiO2

    SciTech Connect

    Sanz, J.; Rojo, J.M.

    1985-11-07

    The adsorption of hydrogen on reduced Cl3Rh/TiO2 catalysts originates a new line in the NMR spectrum, shifted toward high fields, that has been ascribed to hydrogen adsorbed on metal particles. The analysis of the intensity and position of this line vs. the H2 pressure indicates the presence of two types of adsorbed hydrogen on the metal and the modification of the metal-hydrogen interaction with the extent of the adsorption. The reduction of the sample at temperatures above 723 K produces a drop of the shifted line intensity, indicating the appearance of the strong metal-support interaction, but a subsequent reoxidation treatment permits to recover the intensity of this line and eliminates the SMSI effect. The adsorption of the most labile hydrogen on the metal is accompanied by a hydrogen transfer to the support, which is reflected in the NMR spectra of the oxidized sample as an intensity increase of the unshifted line with the H2 pressure. The incorporation of hydrogen to the support is favored when the temperature of the sample is increased above 400 K. 14 references, 8 figures, 1 table.

  20. Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

    NASA Technical Reports Server (NTRS)

    Coplen, T. B.; Hanshaw, B. B.

    1973-01-01

    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

  1. Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

    NASA Technical Reports Server (NTRS)

    Coplen, T. B.; Hanshaw, B. B.

    1973-01-01

    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

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

    PubMed

    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

  3. Isotope Effects in Collisional VT Relaxation of Molecular Hydrogen

    NASA Technical Reports Server (NTRS)

    Bieniek, R. J.

    2006-01-01

    A simple exponential-potential model of molecular collisions leads to a two-parameter analytic expression for rates of collisionally induced vibrational-translation (VT) energy exchange that has been shown to be accurate over variations of orders of magnitude as a function of temperature in a variety of systems. This includes excellent agreement with reported experimental and theoretical results for the fundamental self-relaxation rate of molecular hydrogen H2(v = 1) + H2 yields H2(v = 0) + H2. The analytic rate successfully follows the five-orders-of-magnitude change in experimental values for the temperature range 50-2000 K. This approach is now applied to isotope effects in the vibrational relaxation rates of excited HD and D2 in collision with H2: HD(v = 1)+H2 yields HD(v = 0)+H2 and D2(v = 1)+H2 yields D2(v = 0)+H2. The simplicity of the analytic expression for the thermal rate lends itself to convenient application in modeling the evolving vibrational populations of molecular hydrogen in shocked astrophysical environments.

  4. Round robin analyses of hydrogen isotope thin films standards.

    SciTech Connect

    Browning, James Frederick; Doyle, Barney Lee; Wampler, William R.; Wetteland, C. J.; LaDuca, Carol A.; Banks, James Clifford; Wang, Y. Q.; Tesmer, Joseph R.

    2003-06-01

    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.

  5. Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

    SciTech Connect

    Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2008-12-01

    Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.

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

    SciTech Connect

    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. Aniline adsorption, hydrogenation, and hydrogenolysis on the Ni(100) surface

    SciTech Connect

    Huang, S.X.; Gland, J.L.; Fischer, D.A.

    1996-06-13

    The bonding and reactions of adsorbed aniline have been characterized on the Ni(100) surface both in hydrogen and in vacuum with a combination of surface spectroscopies. The structure of adsorbed aniline and derived intermediates has been characterized by near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoemission spectroscopy (XPS). The dominant surface reactions have been studied using temperature-programmed reaction spectroscopy (TPRS) and in-situ temperature-programmed fluorescence yield near- edge spectroscopy (TP FYNES). Competition between hydrogenation, hydrogenolysis, and dehydrogenation of aniline in the 300-400 K temperature range depends markedly on hydrogen pressures in the vacuum to 0.01 Torr range. In the absence of external hydrogen, dehydrogenation dominates with increasing temperature. Both hydrogenation and hydrogenolysis of aniline-derived surface intermediates are enhanced dramatically by hydrogen atmospheres. For aniline coverages up to 1 monolayer, hydrogenolysis to form benzene at 475 K is dominant over a broad hydrogen pressure range (> 10{sup -6} Torr). Ultrasoft X-ray absorption spectra above the carbon K edge of the aniline-derived surface intermediates reveal that the precursor for hydrogenolysis is a hydrogenated aniline-derived species indistinguishable from cyclohexylamine. 34 refs., 12 figs., 2 tabs.

  8. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  9. Atomic hydrogen adsorption and incipient hydrogenation of the Mg(0001) surface: a density-functional theory study.

    PubMed

    Li, Yanfang; Zhang, Ping; Sun, Bo; Yang, Yu; Wei, Yinghui

    2009-07-21

    We investigate the atomic hydrogen adsorption on Mg(0001) by using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics is systematically studied for a wide range of coverage Theta [from 0.11 to 2.0 monolayers (ML)] and adsorption sites. In the coverage range 0 < Theta < 1.0, the most stable among all possible adsorption sites is the on-surface fcc site followed by the hcp site, and the binding energy increases with the coverage, thus indicating the higher stability of on-surface adsorption and a tendency to the formation of H islands (clusters) when increasing the coverage within the region 0 < Theta < 1.0. The on-surface diffusion path energetics of atomic hydrogen as well as the activation barriers for hydrogen penetration from the on-surface to the subsurface sites are also presented at low coverage. At high coverage of 1.0 < Theta < or = 2.0, it is found that the coadsorption configuration with 1.0 monolayer of H residing on the surface fcc sites and the remaining (Theta-1.0) monolayer of H occupying the subsurface tetra-I sites is most energetically favorable. The resultant H-Mg-H sandwich structure for this most stable coadsorption configuration displays similar spectral features to the bulk hydride MgH(2) in the density of states. The other properties of the H/Mg(0001) system including the charge distribution, the lattice relaxation, the work function, and the electronic density of states are also studied and discussed in detail. It is pointed out that the H-Mg chemical bonding during surface hydrogenation displays a mixed ionic/covalent character.

  10. Hydrogen adsorption in the NaA zeolite: A comparison between numerical simulations and experiments

    NASA Astrophysics Data System (ADS)

    Darkrim, Farida; Aoufi, Asdin; Malbrunot, Pierre; Levesque, Dominique

    2000-04-01

    At room temperature and high pressures between 10 MPa and 140 MPa, hydrogen adsorption in the NaA zeolite was studied by grand canonical Monte Carlo simulation. The computed values of the average number of hydrogen molecules adsorbed in a crystal unit were compared to those measured at the same temperature and pressures between 10 MPa and 70 MPa. A quantitative agreement between the two sets of values was obtained by using, in the simulations, a model of zeolite crystal where the Al, Si, O, and Na atoms, disposed in accordance with the crystallographic structure of the NaA zeolite determined by x-ray diffraction, had effective electric charges and were sources of a van der Waals interaction. The adsorption of hydrogen molecules in the NaA zeolite resulted from the combined effects of van der Waals interactions and polarization of hydrogen molecules induced by the electric field of the effective charges.

  11. Quantifying residual hydrogen adsorption in low-temperature STMs

    NASA Astrophysics Data System (ADS)

    Natterer, F. D.; Patthey, F.; Brune, H.

    2013-09-01

    We report on low-temperature scanning tunneling microscopy observations demonstrating that individual Ti atoms on hexagonal boron nitride dissociate and adsorb hydrogen without measurable reaction barrier. The clean and hydrogenated states of the adatoms are clearly discerned by their apparent height and their differential conductance revealing the Kondo effect upon hydrogenation. Measurements at 50 K and 5 × 10- 11 mbar indicate a sizable hydrogenation within only 1 h originating from the residual gas pressure, whereas measurements at 4.7 K can be carried out for days without H2 contamination problems. However, heating up a low-T STM to operate it at variable temperature results in very sudden hydrogenation at around 17 K that correlates with a sharp peak in the total chamber pressure. From a quantitative analysis we derive the desorption energies of H2 on the cryostat walls. We find evidence for hydrogen contamination also during Ti evaporation and propose a strategy on how to dose transition metal atoms in the cleanliest fashion. The present contribution raises awareness of hydrogenation under seemingly ideal ultra-high vacuum conditions, it quantifies the H2 uptake by isolated transition metal atoms and its thermal desorption from the gold plated cryostat walls.

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

    SciTech Connect

    Ward, Donald K.; Zhou, Xiaowang; Karnesky, Richard A.; Kolasinski, Robert; Foster, Michael E.; Thurmer, Konrad; Chao, Paul; Epperly, Ethan Nicholas; Zimmerman, Jonathan A.; Wong, Bryan M.; Sills, Ryan B.

    2015-09-01

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

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

    SciTech Connect

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

    2008-07-15

    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)

  14. High-capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework.

    PubMed

    Xiao, Bo; Wheatley, Paul S; Zhao, Xuebo; Fletcher, Ashleigh J; Fox, Sarah; Rossi, Adriano G; Megson, Ian L; Bordiga, S; Regli, L; Thomas, K Mark; Morris, Russell E

    2007-02-07

    Gas adsorption experiments have been carried out on a copper benzene tricarboxylate metal-organic framework material, HKUST-1. Hydrogen adsorption at 1 and 10 bar (both 77 K) gives an adsorption capacity of 11.16 mmol H2 per g of HKUST-1 (22.7 mg g(-)1, 2.27 wt %) at 1 bar and 18 mmol per g (36.28 mg g(-)1, 3.6 wt %) at 10 bar. Adsorption of D2 at 1 bar (77 K) is between 1.09 (at 1 bar) and 1.20(at <100 mbar) times the H2 values depending on the pressure, agreeing with the theoretical expectations. Gravimetric adsorption measurements of NO on HKUST-1 at 196 K (1 bar) gives a large adsorption capacity of approximately 9 mmol g(-1), which is significantly greater than any other adsorption capacity reported on a porous solid. At 298 K the adsorption capacity at 1 bar is just over 3 mmol g(-1). Infra red experiments show that the NO binds to the empty copper metal sites in HKUST-1. Chemiluminescence and platelet aggregometry experiments indicate that the amount of NO recovered on exposure of the resulting complex to water is enough to be biologically active, completely inhibiting platelet aggregation in platelet rich plasma.

  15. A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

    USGS Publications Warehouse

    Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

    2015-01-01

    This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

  16. Enhancing the interaction strength and capacities of hydrogen storage via surface adsorption

    NASA Astrophysics Data System (ADS)

    Brown, Craig

    2008-03-01

    Storing Hydrogen molecules in porous media based on a physisorption mechanism is one possible approach to reach the US Department of Energy targets for on-board hydrogen storage. Although the storage capacities of metal-organic frameworks (MOFs) have progressed significantly over recent years, some technological obstacles pose challenges for their future improvement. These include the generally low H2 adsorption enthalpy limiting room temperature applications and the lack of understanding of surface packing density hindering the efficient improvement of H2 adsorption uptake. To improve the H2 affinity in MOFs, our previous work has shown that the coordinatively unsaturated metal centers (CUMCs) can greatly enhance the H2 binding strength. Our current study of MOF-74 will be presented, showing that its open Zn^2+ ions bind H2 strongly and are identified as being responsible for the large initial H2 adsorption enthalpy of 8.4 kJ/mol. In all, there are four H2 adsorption sites in MOF-74 identified by neutron powder diffraction. These four hydrogen adsorption sites are closely packed in MOF-74 and form a one dimensional nanoscale tube structure. We also demonstrate an interesting correlation that MOFs with CUMCs generally show larger surface packing densities than that of other MOFs without CUMCs. The implications of this will be addressed.

  17. Hydrogen sulfide adsorption on MOFs and MOF/graphite oxide composites.

    PubMed

    Petit, Camille; Mendoza, Barbara; Bandosz, Teresa J

    2010-12-03

    Composites of a copper-based metal-organic framework (MOF) and graphite oxide (GO) were tested for hydrogen sulfide removal at ambient conditions. In order to understand the mechanisms of adsorption, the initial and exhausted samples were analyzed by various techniques including X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analyses, and sorption of nitrogen. Compared to the parent materials, an enhancement in hydrogen sulfide adsorption was found. It was the result of physical adsorption of water and H(2)S in the pore space formed at the interface between the MOF units and the graphene layers where the dispersive forces are the strongest. Besides physisorption, reactive adsorption was found as the main mechanism of retention. H(2)S molecules bind to the copper centers of the MOF. They progressively react with the MOF units resulting in the formation of copper sulfide. This leads to the collapse of the MOF structure. Water enhances adsorption in the composites as it allows the dissolution of hydrogen sulfide.

  18. Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Tetrahymena thermophila, Dunaliella bardawil and Haloarcula marismortui

    NASA Astrophysics Data System (ADS)

    Dirghangi, S. S.; Pagani, M.

    2008-12-01

    Paleoclimatological research is mainly based on proxies that reflect different climatic variations. Organic compounds preserved in sediments form a very important group of proxies, of which lipids are an important class. Recently, attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis given its potential as a proxy for understanding changes in the hydrological system. Hydrogen isotope ratios of lipids depend on hydrogen isotopic composition of the ambient water, which in turn is dependent on hydrological conditions. Hydrogen isotope ratios of lipids also depend on the biosynthetic pathway, which causes differences between hydrogen isotope ratios of lipids synthesized by different organisms. The application of lipids derived from multiple source organisms (e.g. fatty acids) are less useful for reconstructing hydrogen isotopic compositions of ambient water, because of the lack of specificity regarding its source. On the other hand, lipids that are synthesized by specific kinds of organisms or lipids that in a specific environment are synthesized by specific kinds of organisms are more useful for reconstructing hydrogen isotopic compositions of the ambient water. For this study, we are investigating the hydrogen isotope fractionation between ambient water and lipids that are derived from specific organisms from hypersaline environments. Specifically, we have grown three organisms that are abundant in saline to hypersaline environments, including Tetrahymena thermophila (Protozoa), Dunaliella bardawil (Alga), and Haloarcula marismortui (Archaea) in pure cultures and are in the process of evaluating isotopic variability of specific lipids (i.e. Tetrahymanol in Tetrahymena, beta-carotene and Stigmasterol in Dunaliella, and archaeol in Haloarcula) and other non-specific fatty acids associated with the D/H composition of ambient water, growth temperature and salinity.

  19. How atmospheric CO2 concentrations can affect the hydrogen isotope composition of plant organic compounds

    NASA Astrophysics Data System (ADS)

    Cormier, M. A.; Werner, R. A.; Kahmen, A.

    2016-12-01

    In contrast to the stable carbon, nitrogen and oxygen isotope composition of plant materials, the hydrogen isotope composition of plant organic compounds has not yet been established as a tool in ecological or biogeochemical research. With the development of new analytical instruments that allow the hydrogen isotope analysis of selected plant compounds there is, however, a growing interest to explore the power of hydrogen isotopes as tools for ecological and biogeochemical research. In my presentation, I will summarize recent works from greenhouse experiments showing how, mechanistically, the CO2 concentrations in the atmosphere can affect the hydrogen isotope composition of lipids and cellulose via the carbon and energy metabolism in plants: Our experiments revealed that plants growing under lower atmospheric CO2 concentrations (i.e. 140 ppm) are generally 2H enriched compared to plants growing in contemporary and even higher atmospheric CO2 concentrations (i.e. 400 and 800 ppm). We were able to identify various biochemical processes during the biosynthesis of plant tissue that contribute to these patterns and hope that this will help to establish hydrogen isotope composition of plant derived compounds as a robust proxy for the carbon and energy metabolism in plants that could serve as an important new tool in plant ecology, biogeochemistry and paleoclimatology. This new insight in the biosynthetic fractionation of hydrogen isotopes in plants might also explain a large amount of the scatter observed when looking at the relation between the precipitation and the leaf wax n-alkanes hydrogen isotope composition. This might be particularly relevant for paleo-hydrological studies using hydrogen isotopes in geological transitions where the atmospheric CO2 concentrations vary significantly such as during the glacial-interglacial transitions.

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

    SciTech Connect

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

    1993-07-01

    Resonant ultrasound spectroscopy has been used to investigate ultrasonic attenuation in single crystals of Sc, ScH[sub 0.25], and ScD[sub 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[sub 0.25] and near 50 K for ScD[sub 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[sub 0.25] than in ScD[sub 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 [ital c] axes. The results are consistent with an isotope-independent strength for the coupling of the TLS to the ultrasound.

  1. An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite compounds.

    PubMed

    Cheng, Hansong; Sha, Xianwei; Chen, Liang; Cooper, Alan C; Foo, Maw-Lin; Lau, Garret C; Bailey, Wade H; Pez, Guido P

    2009-12-16

    We present a combined theoretical and experimental study on H(2) physisorption in partially fluorinated graphite. This material, first predicted computationally using ab initio molecular dynamics simulation and subsequently synthesized and characterized experimentally, represents a novel class of "acceptor type" graphite intercalated compounds that exhibit significantly higher isosteric heat of adsorption for H(2) at near ambient temperatures than previously demonstrated for commonly available porous carbon-based materials. The unusually strong interaction arises from the semi-ionic nature of the C-F bonds. Although a high H(2) storage capacity (>4 wt %) at room temperature is predicted not to be feasible due to the low heat of adsorption, enhanced storage properties can be envisaged by doping the graphitic host with appropriate species to promote higher levels of charge transfer from graphene to F(-) anions.

  2. Understanding Volumetric and Gravimetric Hydrogen Adsorption Trade-off in Metal-Organic Frameworks.

    PubMed

    Gómez-Gualdrón, Diego A; Wang, Timothy C; García-Holley, Paula; Sawelewa, Ruth M; Argueta, Edwin; Snurr, Randall Q; Hupp, Joseph T; Yildirim, Taner; Farha, Omar K

    2017-04-07

    Metal-organic frameworks (MOFs) are porous crystalline materials that are promising for adsorption-based, on-board storage of hydrogen in fuel-cell vehicles. Volumetric and gravimetric hydrogen capacities are the key factors that determine the size and weight of the MOF-filled tank required to store a certain amount of hydrogen for reasonable driving range. Therefore, they must be optimized so the tank is neither too large nor too heavy. Because the goals of maximizing MOF volumetric and gravimetric hydrogen adsorption loadings individually are incompatible, an in-depth understanding of the trade-off between MOF volumetric and gravimetric loadings is necessary to achieve the best compromise between these properties. Here we study, both experimentally and computationally, the trade-off between volumetric and gravimetric cryo-adsorbed hydrogen deliverable capacity by taking an isoreticular series of highly stable zirconium MOFs, NU-1101, NU-1102, and NU-1103 as a case study. These MOFs were studied under recently proposed operating conditions: 77 K/100 bar →160 K/5 bar. We found the difference between highest and lowest measured deliverable capacity in the MOF series to be ca. 40% gravimetrically, but only ca. 10% volumetrically. From our molecular simulation results, we found hydrogen "monolayer" adsorption to be proportional to the surface area, whereas hydrogen "pore filling" adsorption is proportional to the pore volume. Thus, we found that the higher variability in gravimetric deliverable capacity in contrast to the volumetric capacity, occurs due to the proportional relation between gravimetric surface area and pore volume in the NU-110x series in contrast to the inverse relation between volumetric surface area and void fraction. Additionally, we find better correlations with geometric surface areas than with BET areas. NU-1101 presents the highest measured volumetric performance with 46.6 g/L (9.1 wt %), whereas NU-1103 presents the highest gravimetric one

  3. Hydrogen adsorption in the series of carbon nanostructures: Graphenes-graphene nanotubes-nanocrystallites

    NASA Astrophysics Data System (ADS)

    Soldatov, A. P.; Kirichenko, A. N.; Tat'yanin, E. V.

    2016-07-01

    A comparative analysis of hydrogen absorption capability is performed for the first time for three types of carbon nanostructures: graphenes, oriented carbon nanotubes with graphene walls (OCNTGs), and pyrocarbon nanocrystallites (PCNs) synthesized in the pores of TRUMEM ultrafiltration membranes with mean diameters ( D m) of 50 and 90 nm, using methane as the pyrolized gas. The morphology of the carbon nanostructures is studied by means of powder X-ray diffraction, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM). Hydrogen adsorption is investigated via thermogravimetric analysis (TGA) in combination with mass-spectrometry. It is shown that only OCNTGs can adsorb and store hydrogen, the desorption of which under atmospheric pressure occurs at a temperature of around 175°C. Hydrogen adsorption by OCNTGs is quantitatively determined and found to be about 1.5% of their mass. Applying certain assumptions, the relationship between the mass of carbon required for the formation of single-wall OCNTGs in membrane pores and the surface area of pores is established. Numerical factor Ψ = m dep/ m calc, where m dep is the actual mass of carbon deposited upon the formation of OCNTGs and mcalc is the calculated mass of carbon necessary for the formation of OCNTGs is introduced. It is found that the dependence of specific hydrogen adsorption on the magnitude of the factor has a maximum at Ψ = 1.2, and OCNTGs can adsorb and store hydrogen in the interval 0.4 to 0.6 < Ψ < 1.5 to 1.7. Possible mechanisms of hydrogen adsorption and its relationship to the structure of carbon nanoformations are examined.

  4. Experimental Evidence for Hydrogen Tunneling when the Isotopic Arrhenius Prefactor (AH/AD) is Unity

    PubMed Central

    Sharma, Sudhir C.; Klinman, Judith P.

    2009-01-01

    The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (AH/AD) of unity are generally ascribed to a semi-classical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an AH/AD of unity and highly elevated (non-classical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semi-classical model based solely on an Arrhenius prefactor ratio. PMID:19061319

  5. Carbon and hydrogen isotope fractionation of benzene and toluene during hydrophobic sorption in multistep batch experiments.

    PubMed

    Imfeld, G; Kopinke, F-D; Fischer, A; Richnow, H-H

    2014-07-01

    The application of compound-specific stable isotope analysis (CSIA) for evaluating degradation of organic pollutants in the field implies that other processes affecting pollutant concentration are minor with respect to isotope fractionation. Sorption is associated with minor isotope fractionation and pollutants may undergo successive sorption-desorption steps during their migration in aquifers. However, little is known about isotope fractionation of BTEX compounds after consecutive sorption steps. Here, we show that partitioning of benzene and toluene between water and organic sorbents (i.e. 1-octanol, dichloromethane, cyclohexane, hexanoic acid and Amberlite XAD-2) generally exhibits very small carbon and hydrogen isotope effects in multistep batch experiments. However, carbon and hydrogen isotope fractionation was observed for the benzene-octanol pair after several sorption steps (Δδ(13)C=1.6 ± 0.3‰ and Δδ(2)H=88 ± 3‰), yielding isotope fractionation factors of αC=1.0030 ± 0.0005 and αH=1.195 ± 0.026. Our results indicate that the cumulative effect of successive hydrophobic partitioning steps in an aquifer generally results in insignificant isotope fractionation for benzene and toluene. However, significant carbon and hydrogen isotope fractionation cannot be excluded for specific sorbate-sorbent pairs, such as sorbates with π-electrons and sorbents with OH-groups. Consequently, functional groups of sedimentary organic matter (SOM) may specifically interact with BTEX compounds migrating in an aquifer, thereby resulting in potentially relevant isotope fractionation.

  6. A model predicting hydrogen and oxygen isotopes of mammalian hair at the landscape scale

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.; Podlesak, D.; Cerling, T.; Chesson, L.; Bowen, G.

    2006-12-01

    A model has been developed to predict hydrogen and oxygen isotope ratios of keratin in hair of mammalian herbivores and omnivores, incorporating the influences of drinking water and dietary input. The isotopic composition of carbohydrates in food sources and the water in blood and tissues are predicted as intermediate components linking drinking water and dietary sources (environment) with hair (environmental recorder). This model is scaled to landscape and regional levels using geographic information system map predictions of the hydrogen and oxygen isotope ratios of drinking waters and anticipated hydrogen and oxygen isotope ratios of carbohydrate food sources. The model was tested using isotope ratios of human hair (an omnivore) from across the USA. We discuss the application of this model as a tool for providing spatially integrated information about the quality of primary productivity relevant to mammalian herbivores over time, through the effects of varying primary productivity on protein nitrogen balance of the herbivore.

  7. Isotope effects on chemical shifts in the study of intramolecular hydrogen bonds.

    PubMed

    Hansen, Poul Erik

    2015-01-30

    The paper deals with the use of isotope effects on chemical shifts in characterizing intramolecular hydrogen bonds. Both so-called resonance-assisted (RAHB) and non-RAHB systems are treated. The importance of RAHB will be discussed. Another very important issue is the borderline between "static" and tautomeric systems. Isotope effects on chemical shifts are particularly useful in such studies. All kinds of intramolecular hydrogen bonded systems will be treated, typical hydrogen bond donors: OH, NH, SH and NH+, typical acceptors C=O, C=N, C=S C=N-. The paper will be deal with both secondary and primary isotope effects on chemical shifts. These two types of isotope effects monitor the same hydrogen bond, but from different angles.

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

    Treesearch

    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...

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

    PubMed

    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.

  10. Hydrogen Adsorption Studies Using Surface Acoustic Waves on Nanoparticles

    SciTech Connect

    A.B. Phillips; G. Myneni; B.S. Shivaram

    2005-06-13

    Vanadium nanoparticles, on the order of 20 nm, were deposited on a quartz crystal surface acoustic wave resonator (SAW) using a Nd:YAG pulsed laser deposition system. Due to the high Q and resonant frequency of the SAW, mass changes on the order of 0.1 nanogram can be quantitatively measured. Roughly 60 nanogram of V was deposited on the SAW for these experiments. The SAW was then moved into a hydrogen high pressure cell.At room temperature and 1 atmosphere of hydrogen pressure, 1 wt% H, or H/V {approx} 0.5 (atomic ratio) absorption was measured.

  11. Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: implications for planetary accretion.

    PubMed

    Tyburczy, J A; Krishnamurthy, R V; Epstein, S; Ahrens, T J

    1990-05-01

    The degree of impact-induced devolatilization of nonporous serpentine, porous serpentine, and deuterium-enriched serpentine was investigated using two independent experimental methods, the gas recovery method and the solid recovery method, yielding consistent results. The gas recovery method enables determination of the chemical and hydrogen isotopic composition of the recovered gases. Experiments on deuterium-enriched serpentine unambiguously identify the samples as the source of the recovered gases, as opposed to other possible contaminants. For shock pressures near incipient devolatilization (Pinitial = 5.0 GPa), the hydrogen isotopic composition of the evolved gas is similar to that of the starting material. For higher shock pressures the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. The hydrogen isotopic fractionation between the evolved gas and the residual solid indicates nonequilibrium, kinetic control of gas-solid isotopic ratios. In contrast, gaseous H2O-H2 isotopic fractionation suggests high temperature (800-1300 K) isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition (i.e., shear bands). Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can affect the distribution of hydrogen isotopes of planetary bodies during accretion, leaving the interiors enriched in deuterium. The significance of this process for planetary development depends on the models used for extrapolation of the observed isotopic fractionation to devolatilizations greater than those investigated experimentally and assumptions about timing and rates of protoatmosphere loss, frequency of multiple impacts, and rates of gas-solid or gas-melt isotopic re

  12. Ab initio study of adsorption of molecular hydrogen on microporous metal-organic frameworks.

    NASA Astrophysics Data System (ADS)

    Hamel, Sébastien; Côté, Michel

    2004-03-01

    In the ongoing search for promising compounds for hydrogen storage, novel porous metal-organic frameworks (MOF) have been discovered recently [1]. Well defined binding sites were deduced from inelastic neutron scattering (INS) spectroscopy of the rotational transitions of the adsorbed molecular hydrogen. In light of this discovery we performed ab initio density functional theory (DFT) calculations of the adsorption of molecular hydrogen on this class of microporous MOF to compare different adsorption sites. Different approximations for the exchange-correlation potentials were accessed for a set of relevant properties such as binding energy, energetically favored configuration and distance between the adsorbents and adsorbates. In particular, theoretical rotational spectra of the adsorbed H2 were obtained that could be compared to the experimental INS spectra. [1] Rosi et al., Science Vol. 300, 1127 (2003)

  13. Hydrogen adsorption on Ru(001) studied by Scanning TunnelingMicroscopy

    SciTech Connect

    Tatarkhanov, Mous; Rose, Franck; Fomin, Evgeny; Ogletree, D.Frank; Salmeron, Miquel

    2008-01-18

    The adsorption of hydrogen on Ru(001) was studied by scanning tunneling microscopy at temperatures around 50 K. Hydrogen was found to adsorb dissociatively forming different ordered structures as a function of coverage. In order of increasing coverage {theta} in monolayers (ML) these were ({radical}3 x {radical}3)r30{sup o} at {theta} = 0.3 ML; (2 x 1) at {theta} = 0.50 ML, (2 x 2)-3H at {theta} = 0.75, and (1 x 1) at {theta} = 1.00. Some of these structures were observed to coexist at intermediate coverage values. Close to saturation of 1 ML, H-vacancies (unoccupied three fold fcc hollow Ru sites) were observed either as single entities or forming transient aggregations. These vacancies diffuse and aggregate to form active sites for the dissociative adsorption of hydrogen.

  14. SAMPEX observations of energetic hydrogen isotopes in the inner zone.

    PubMed

    Looper, M D; Blake, J B; Cummings, J R; Mewaldt, R A

    1996-11-01

    We report observations of geomagnetically-trapped hydrogen isotopes at low altitudes, near the feet of field lines in the inner zone, made with the PET instrument aboard the SAMPEX satellite. We have mapped protons from 19 to 500 MeV, and have discovered a collocated belt of deuterons, which we have mapped from 18 to 58 MeV/nucleon. We found deuterium at about 1% of the level of the proton flux at the same energy per nucleon, and no tritium at energies of tens of MeV/nucleon with an upper limit of about 0.1% of the proton flux. Protons and deuterons showed similar time dependence, with fluxes approximately tripling from July 1992 to March 1996, and similar pitch-angle dependence. The high-L limits of the proton and deuteron belts as functions of energy were organized by rigidity, as was to be expected if these limits were set for both species by inability of particles to sustain adiabatic motion and stable trapping.

  15. SAMPEX observations of energetic hydrogen isotopes in the inner zone

    NASA Technical Reports Server (NTRS)

    Looper, M. D.; Blake, J. B.; Cummings, J. R.; Mewaldt, R. A.

    1996-01-01

    We report observations of geomagnetically-trapped hydrogen isotopes at low altitudes, near the feet of field lines in the inner zone, made with the PET instrument aboard the SAMPEX satellite. We have mapped protons from 19 to 500 MeV, and have discovered a collocated belt of deuterons, which we have mapped from 18 to 58 MeV/nucleon. We found deuterium at about 1% of the level of the proton flux at the same energy per nucleon, and no tritium at energies of tens of MeV/nucleon with an upper limit of about 0.1% of the proton flux. Protons and deuterons showed similar time dependence, with fluxes approximately tripling from July 1992 to March 1996, and similar pitch-angle dependence. The high-L limits of the proton and deuteron belts as functions of energy were organized by rigidity, as was to be expected if these limits were set for both species by inability of particles to sustain adiabatic motion and stable trapping.

  16. Relation between hydrogen isotopic ratios of bone collagen and rain

    SciTech Connect

    Cormie, A.B.; Schwarcz, H.P. ); Gray, J. )

    1994-01-01

    The hydrogen isotopic value ([delta]D) of deer bone collagen is related to both [delta]D of rain during the growing season and growing season relative humidity (RH). With correction for the effects of RH, bone [delta]D is related to growing season rain [delta]D in a simple manner with a slope of 1.0. This indicates that, with RH correction, there are no additional sources of bias in the [delta]D of bone due to unaccounted for biologic or climatic effects. Due to a low sensitivity of bone [delta]D to RH effects, both yearly and growing season rain [delta]D can be estimated with considerable accuracy (R = 0.97 and R = 0.96) from bone collagen [delta]D and [delta][sup 15]N. Here, [delta][sup 15]N is used to correct bone [delta]D for the effects of RH. From these estimates of rain [delta]D, it may then be possible to evaluate temperature since the [delta]D of rain primarily reflects local temperature. Therefore, the measurement of bone collagen [delta]D has good potential for evaluating paleoclimates.

  17. In situ monitoring hydrogen isotope retention in ITER first wall

    NASA Astrophysics Data System (ADS)

    Mukhin, E. E.; Andrew, P.; Anthoine, A. D.; Bazhenov, A. N.; Barnsley, R.; Bukreev, I. M.; Bukhovets, V. L.; Chernakov, A. P.; Gorodetsky, A. E.; Kochergin, M. M.; Koval, A. N.; Kukushkin, A. B.; Kukushkin, A. S.; Kurskiev, G. S.; Levashova, M. G.; Litvinov, A. E.; Litunovsky, V. N.; Markin, A. V.; Mazul, I. V.; Masyukevich, S. V.; Miroshnikov, I. V.; Nemov, A. S.; Novokhatsky, A. N.; Razdobarin, A. G.; Sherstnev, E. V.; Samsonov, D. S.; Semenov, V. V.; Smirnov, A. S.; De Temmerman, G.; Tolstyakov, S. Yu.; Zalavutdinov, R. Kh.; Walsh, M. J.

    2016-03-01

    Tritium retention inside the vacuum vessel is a potentially serious constraint in the operation of large-scale fusion machines like ITER. An in situ diagnostics for first wall H/D/T retention by laser induced desorption spectroscopy (LIDS) is proposed for use between plasma discharges. The technique is based on local baking of the first wall by laser irradiation and subsequent analysis of the in-vessel gas by optical emission spectroscopy of plasma radiation. The local heating implementation, kinetics of H/D/T thermal extraction and the accuracy of optical emission spectroscopy measurements are analysed. To resolve the H/D/T lines spectroscopically, their thermal broadening should be minimized to prevent overlapping of the line shapes. A comparative performance analysis of several types of plasma sources with relatively cold ions is made including the following types of discharges: Penning, RF multipactor, laser torch and ECR. All these radiation sources require rather low power and could be used for remote in situ measurements of relative densities of the thermally extracted hydrogen isotopes.

  18. Hydrogen isotope trapping in Al-Cu binary alloys

    DOE PAGES

    Chao, Paul; Karnesky, Richard A.

    2016-01-01

    In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol–1 (0.19 ± 0.03 eV). Typical occupancy of this trap is high;more » for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D2 for 68 days, there is ca. there is 3.15×10–7 mol D bound to the precipitate trap per mol of Al, accounting for a third of the D in the charged sample.« less

  19. Hydrogen isotope trapping in Al-Cu binary alloys

    SciTech Connect

    Chao, Paul; Karnesky, Richard A.

    2016-01-01

    In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol–1 (0.19 ± 0.03 eV). Typical occupancy of this trap is high; for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D2 for 68 days, there is ca. there is 3.15×10–7 mol D bound to the precipitate trap per mol of Al, accounting for a third of the D in the charged sample.

  20. SAMPEX observations of energetic hydrogen isotopes in the inner zone

    NASA Technical Reports Server (NTRS)

    Looper, M. D.; Blake, J. B.; Cummings, J. R.; Mewaldt, R. A.

    1996-01-01

    We report observations of geomagnetically-trapped hydrogen isotopes at low altitudes, near the feet of field lines in the inner zone, made with the PET instrument aboard the SAMPEX satellite. We have mapped protons from 19 to 500 MeV, and have discovered a collocated belt of deuterons, which we have mapped from 18 to 58 MeV/nucleon. We found deuterium at about 1% of the level of the proton flux at the same energy per nucleon, and no tritium at energies of tens of MeV/nucleon with an upper limit of about 0.1% of the proton flux. Protons and deuterons showed similar time dependence, with fluxes approximately tripling from July 1992 to March 1996, and similar pitch-angle dependence. The high-L limits of the proton and deuteron belts as functions of energy were organized by rigidity, as was to be expected if these limits were set for both species by inability of particles to sustain adiabatic motion and stable trapping.

  1. Use of magnesium for recovering hydrogen isotopes from tritiated water

    SciTech Connect

    Willms, R.S.; Konishi, Satoshi; Okuno, Kenji

    1994-07-01

    Reacting tritiated water with hot metal to recover the tritium from tritiated water has been practiced for considerable time. A metal frequently used for this purpose has been uranium. Recent work at the Tritium Systems Test Assembly at Los Alamos National Laboratory has focused on using magnesium for this purpose. This work was done as part of the Annex IV collaboration between the US Department of Energy/TSTA and the Japan Atomic Energy Research Institute/Tritium Processing Laboratory. Magnesium appears to have reactive properties that are as good as uranium and possibly better, and, of course, magnesium is easier to handle and less strictly controlled. Both bench-scale and practical-scale experiments were conducted with magnesium, including tests with tritiated water. Mg bed construction techniques and operating parameters were determined. Testing showed that the Mg packed bed was very effective for recovering hydrogen isotopes from water. However, when used for this purpose either Mg or U is irreversibly consumed and must be disposed of as tritiated waste. It follows tat this processing technique would be inappropriate for a large tritiated water processing operation. However, this technique may find utility for small-scale systems.

  2. Hydrogen isotope accumulation in the helium implantation zone in tungsten

    NASA Astrophysics Data System (ADS)

    Markelj, S.; Schwarz-Selinger, T.; Založnik, A.

    2017-06-01

    The influence of helium (He) on deuterium (D) transport and retention was studied experimentally in tungsten (W). Helium was implanted 1 µm deep into W to a maximum calculated concentration of 3.4 at.%. To minimize the influence of displacement damage created during the He implantation on D retention, so-called self-damaged W was used. W was damaged by 20 MeV W ion bombardment and defects were populated by low-temperature D plasma at room temperature before He implantation. Deuterium depth profiling was performed in situ during isochronal annealing in the temperature range from 300 K to 800 K. It is shown for the first time unambiguously that He attracts D and locally increases D trapping. Deuterium retention increased by a factor of two as compared to a non-He implanted W reference after sample annealing at 450 K. Rate equation modelling can explain the measured D depth profiles quantitatively when keeping the de-trapping parameters unchanged but only increasing the number of traps in the He zone. This bolsters the confidence in the theoretical calculations predicting that more hydrogen isotopes can be stored around a He cluster zone.

  3. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  4. The dissociative adsorption of hydrogen on defect-'free' Pt(111)

    NASA Astrophysics Data System (ADS)

    Poelsema, Bene; Lenz, Klaus; Comsa, George

    2010-08-01

    The interaction of hydrogen with an (almost) defect-free Pt(111) surface (step density ~ 0.1%) is revisited in a combined thermal energy atom scattering/thermal desorption spectroscopy (TEAS/TDS) study. We propose a novel kinetic precursor-mediated adsorption/desorption model for hydrogen/Pt(111) to reconcile seemingly conflicting results, such as extremely different dissociative adsorption kinetics at 25 and 155 K. Up to a perpendicular energy of (at least) 60 meV, highly relevant for hydrogenation reactions, the initial sticking probability scales with perpendicular energy to the power 1.9. This atypical behaviour is attributed to probing larger corrugation amplitudes at higher normal energy, leading to scattering of hydrogen into a dynamic precursor prior to dissociation and thus to increased trapping. Scrutiny of the data demonstrates that only a small minority of the surface sites (most probably steps) is active in dissociation. The observed decay of the heat of adsorption with coverage indicates strong repulsion between hydrogen atoms. The TDS-spectra of hydrogen from the defect-'free' Pt(111) consist definitively of a single (β2-)peak in contrast to the frequently measured double (β1, β2-)peak structure and at variance with the yet widely accepted conjecture that repulsive interactions lead to double (β1, β2-)peak structures in TDS-spectra. TDS-spectra simulated by applying the micro-reversibility principle and using TEAS-data are in agreement with the experimental ones. The TEAS-data, probing hydrogen whilst on the surface, are thus consistent with TDS-data, probing hydrogen after leaving the surface.

  5. A comparative analysis of the cryo-compression and cryo-adsorption hydrogen storage methods

    SciTech Connect

    Petitpas, G; Benard, P; Klebanoff, L E; Xiao, J; Aceves, S M

    2014-07-01

    While conventional low-pressure LH₂ dewars have existed for decades, advanced methods of cryogenic hydrogen storage have recently been developed. These advanced methods are cryo-compression and cryo-adsorption hydrogen storage, which operate best in the temperature range 30–100 K. We present a comparative analysis of both approaches for cryogenic hydrogen storage, examining how pressure and/or sorbent materials are used to effectively increase onboard H₂ density and dormancy. We start by reviewing some basic aspects of LH₂ properties and conventional means of storing it. From there we describe the cryo-compression and cryo-adsorption hydrogen storage methods, and then explore the relationship between them, clarifying the materials science and physics of the two approaches in trying to solve the same hydrogen storage task (~5–8 kg H₂, typical of light duty vehicles). Assuming that the balance of plant and the available volume for the storage system in the vehicle are identical for both approaches, the comparison focuses on how the respective storage capacities, vessel weight and dormancy vary as a function of temperature, pressure and type of cryo-adsorption material (especially, powder MOF-5 and MIL-101). By performing a comparative analysis, we clarify the science of each approach individually, identify the regimes where the attributes of each can be maximized, elucidate the properties of these systems during refueling, and probe the possible benefits of a combined “hybrid” system with both cryo-adsorption and cryo-compression phenomena operating at the same time. In addition the relationships found between onboard H₂ capacity, pressure vessel and/or sorbent mass and dormancy as a function of rated pressure, type of sorbent material and fueling conditions are useful as general designing guidelines in future engineering efforts using these two hydrogen storage approaches.

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

    USGS Publications Warehouse

    Coplen, T.B.; Qi, H.

    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) ??2H reproducibility (1?? 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. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

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

    USGS Publications Warehouse

    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

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Adsorption of Silica on Synthetic Iron Oxides Fractionates Stable Silicon Isotopes

    NASA Astrophysics Data System (ADS)

    Delstanche, S.; Opfergelt, S.; Cardinal, D.; André, L.; Delvaux, B.

    2006-12-01

    Recent advances show that the quantification of silicon isotopic fractionation by biotic and abiotic processes readily contributes to the understanding of the continental cycle of silicon, involving a.o. Si transfers between aqueous solutions, living organisms and soil minerals. Si uptake by biota, silicate weathering and clay formation all fractionate Si isotopes. Yet, silica may also be quantitatively retrieved from aqueous solutions through specific adsorption of uncharged monosilicic acid (H4SiO4) on oxide surfaces. Iron oxides are ubiquitous in sediments, weathered rocks and soils, where they appear as crystalline and/or short-range ordered (sro) minerals. Here, we report on silicon mass fractionation by H4SiO4 adsorption on two iron oxides: goethite and ferrihydrite. The respective crystalline and sro oxides were synthesized silicon-free and characterized through elementary analysis, selective dissolution, X-ray diffraction and Transmission Electronic Microscopy (TEM). The surface area, as determined by ethylene glycol monoethyl ether (EGME), is 147 m2.g-1 for goethite and 338 m2.g-1 for ferrihydrite. The adsorption of H4SiO4 was measured in batch experiment series designed as function of time (0-504 h) and initial Si concentration in solution (0.2-1.8 mM), at 20°C, constant pH (5.5) and ionic force. The solid:solution ratio was 5g:1000ml. After equilibration, isotopic compositions of 20 selected solution samples were measured on a Nu Plasma Multicollector Mass Spectrometer (MC-ICP-MS) operating in dry plasma mode with external Mg doping. The results were expressed as δ^{29}Si relatively to the NBS28- standard, with an average precision of ± 0.08‰ (± 2σM). With respect to oxide mass but not to EGME-surface area, ferrihydrite (74%) adsorbed more Si than goethite (46%) relatively to initial Si input (at 1.1 mM Si initial concentration after 504 h of contact). Measured against its initial composition (0.00 ± 0.09‰), the equilibrium solution was

  11. Adsorption of ammonia on hydrogen covered GaN(0001) surface - Density Functional Theory study

    NASA Astrophysics Data System (ADS)

    Kempisty, Paweł; Strak, Paweł; Sakowski, Konrad; Krukowski, Stanisław

    2014-09-01

    Density Functional Theory (DFT) simulations of ammonia adsorption at clean and H-covered surface confirmed that ammonia may dissociate into NH2 radical and H adatom or remain in the molecular form. The remaining hydrogen atoms are attached to Ga atoms where the charge transfer to the surface is possible. The calculations show that for the molecular process, the ammonia adsorption energy is close to 2.0 eV, independent of hydrogen coverage. The dissociative process is strongly H-coverage dependent, for low H-coverage the adsorption energy is close to 2.8 eV, for high coverage changes by more than 4 eV reaching negative values. Thus for low coverage the energetically preferred adsorption is dissociative, for high is molecular. The dissociation energy and preferred mode change are related to the change of the Fermi level pinning from Ga broken bond state to valence band maximum (VBM), confirming the decisive role of charge transfer in the adsorption processes.

  12. Adsorption of iodine on hydrogen-reduced silver-exchanged mordenite: Experiments and modeling

    SciTech Connect

    Nan, Yue; Tavlarides, Lawrence L.; DePaoli, David W.

    2016-08-03

    The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag0Z) was studied at the micro-scale. The gas-solid mass transfer and reaction involved in the adsorption process were investigated and evaluated with appropriate models. Optimal conditions for reducing the silver-exchanged mordenite (AgZ) in a hydrogen stream were determined. Kinetic and equilibrium data of iodine adsorption on Ag0Z were obtained by performing single-layer adsorption experiments with experimental systems of high precision at 373–473 K over various iodine concentrations. Results indicate approximately 91% to 97% of the iodine adsorption was through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag0Z was discussed. In conclusion, the Shrinking Core model describes the data well, and the primary rate controlling mechanisms were macro-pore diffusion and silver-iodine reaction. © 2016 American Institute of Chemical Engineers AIChE J, 2016

  13. Adsorption of iodine on hydrogen-reduced silver-exchanged mordenite: Experiments and modeling

    SciTech Connect

    Nan, Yue; Tavlarides, Lawrence L.; DePaoli, David W.

    2016-08-03

    The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag0Z) was studied at the micro-scale. The gas-solid mass transfer and reaction involved in the adsorption process were investigated and evaluated with appropriate models. Optimal conditions for reducing the silver-exchanged mordenite (AgZ) in a hydrogen stream were determined. Kinetic and equilibrium data of iodine adsorption on Ag0Z were obtained by performing single-layer adsorption experiments with experimental systems of high precision at 373–473 K over various iodine concentrations. Results indicate approximately 91% to 97% of the iodine adsorption was through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag0Z was discussed. In conclusion, the Shrinking Core model describes the data well, and the primary rate controlling mechanisms were macro-pore diffusion and silver-iodine reaction. © 2016 American Institute of Chemical Engineers AIChE J, 2016

  14. Adsorption of iodine on hydrogen-reduced silver-exchanged mordenite: Experiments and modeling

    DOE PAGES

    Nan, Yue; Tavlarides, Lawrence L.; DePaoli, David W.

    2016-08-03

    The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag0Z) was studied at the micro-scale. The gas-solid mass transfer and reaction involved in the adsorption process were investigated and evaluated with appropriate models. Optimal conditions for reducing the silver-exchanged mordenite (AgZ) in a hydrogen stream were determined. Kinetic and equilibrium data of iodine adsorption on Ag0Z were obtained by performing single-layer adsorption experiments with experimental systems of high precision at 373–473 K over various iodine concentrations. Results indicate approximately 91% to 97% of the iodine adsorption wasmore » through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag0Z was discussed. In conclusion, the Shrinking Core model describes the data well, and the primary rate controlling mechanisms were macro-pore diffusion and silver-iodine reaction. © 2016 American Institute of Chemical Engineers AIChE J, 2016« less

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Design for hydrogen storage materials via observation of adsorption sites by computer tomography.

    PubMed

    Zhang, Li; Wang, Qi; Liu, Ying-Chun

    2007-05-03

    An effective method denoted as "computer tomography for materials" (mCT) was employed to study the adsorption sites inside metal-organic frameworks (MOFs) at any positions and any view angles. For MOF-5, the first adsorption site alpha(-COO)3 was clearly observed from the mCT images; it locates at the position where three -COO groups joined like a cup. There are four alpha(-COO)3 sites around the Zn4O cluster. Two of them located at the diagonal of the Zn4O cluster are in the same plane "A", whereas the other two equivalent adsorption sites are in another plane "B", which is about 5.4 A away from the plane A. It was found that the electronegativity of oxygen atoms is very important to the adsorption of hydrogen molecules. The hydrogen amount adsorbed in MOFs might be enhanced by introducing some strong electronegative atoms to the organic linkers or frameworks. On the basis of this point of view, five new MOF materials were designed. The adsorbed amounts both in number of hydrogen molecules per unit cell and weight uptake for all of the designed MOFs were calculated. The adsorption amounts of designed MOFs were improved, and the amount for MOF-d5 at 1 bar is as high as 3.7 wt %. It is nearly 5-6 times of that of MOF-5 as a whole. It can be observed that extra adsorption sites were formed in the pores and the effective occupation rate of pore space was obviously improved viewing from the mCT images. These results may give helpful suggestions for the synthetic experimentalists.

  17. Mathematical modelling and simulation on the adsorption of Hydrogen Sulfide (H2S) gas

    NASA Astrophysics Data System (ADS)

    Zulkefli, N. N.; Masdar, M. S.; Isahak, W. R. W.; Jahim, J.; Majlan, E. H.; Rejab, S. A. M.; Lye, C. C.

    2017-06-01

    Hydrogen sulfide, H2S, a pollutant in biofuel gas, i.e., biohydrogen and biomethane, is produced at concentrations ranging from 100 ppm to 10,000 ppm and is recommended to be removed at the early stage of gas purification because it is known as a problematic compound. In this study, adsorption technologies show a promising technique to remove H2S from biofuel gas, which mainly depends on the operating parameters and adsorbent ability. In this study, the development of the models is important to investigate the fundamentals of H2S adsorption mechanism. The fitted mathematics model was performed by considering several assumptions made for fixed-bed adsorption, leading to the determination of the breakthrough curve by solving a set of partial differential equations (PDEs). The operating parameters were as follows: varied inlet concentration at 1000 ppm to 10,000 ppm, flow rate at 0.2 L/min to 0.6 L/min, length bed used at 10 cm to 30 cm, and pressure at 1.5 atm to 5 atm. The adsorption performance was also studied by using commercial activated carbon such as palm kernel shell (PKS-AC), coconut shell activated carbon (coconut shell-AC), and zeolite ZSM-5. To support the effectiveness of the mathematical models, the adsorption test was performed by loading the adsorbent into the fixed-bed adsorption column at an overall diameter of 6 cm and height of 30 cm. The system operated under room temperature, H2S inlet concentration of 1000 ppm, and varying flow rate as in the modelling for PKS-AC. As a result, in the modelling study, the inlet concentration effect was highest in adsorption capacity, breakthrough time, and exhaustion time. However, the increase of flow rate and length bed used only affected the breakthrough and exhaustion times but not adsorption capacity. The total pressure used did not affect adsorption performance. Coconut shell-AC shows longer exhaustion time compared with other adsorbents due to the less frequent changes of adsorbent. In the experimental

  18. Predicting hydrogen and methane adsorption in carbon nanopores for energy storage

    NASA Astrophysics Data System (ADS)

    Ihm, Yungok; Morris, James; Cooper, Valentino; Morris Lab, U. tennessee Collaboration; Advanced material Group, ORNL Collaboration

    2013-03-01

    There are increasing demands for alternate fuels for transportation, which requires safe, high energy density, lightweight storage materials. Experimental measurements and theoretical predictions show relatively low hydrogen storage capacities in various porous materials, limiting hydrogen as a viable alternative for automobiles. In this work, we use a continuum model based on van der Waals density functional (vdW-DF) calculations to elucidate the role that long-range interactions play in the hydrogen adsorption properties of model slit nanopores in carbon. The proper treatment of long-range interactions gives an optimal pore size for hydrogen storage of 8-9 Å (larger than previously predicted). Remarkably, we find a peak hydrogen density close to that of liquid H2 at ambient temperatures, in agreement with recent experimental results on pore-size dependent adsorption in nanoporous carbon. We then show that such nanopores would be better suited to storing methane, possibly providing an alternative to fill the gap between the capacity required by DOE goals and that attainable with current hydrogen storage technology. Research supported by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division.

  19. High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane

    SciTech Connect

    Usvyat, Denis

    2015-09-14

    A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around −3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.

  20. High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane.

    PubMed

    Usvyat, Denis

    2015-09-14

    A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around -3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.

  1. High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane

    NASA Astrophysics Data System (ADS)

    Usvyat, Denis

    2015-09-01

    A multilevel hierarchical ab initio protocol for calculating adsorption on non-conducting surfaces is presented. It employs fully periodic treatment, which reaches local Møller-Plesset perturbation theory of second order (MP2) with correction for the basis set incompleteness via the local F12 technique. Post-MP2 corrections are calculated using finite clusters. That includes the coupled cluster treatment in the local and canonical frameworks (up to perturbative quadruples) and correlated core (with MP2). Using this protocol, the potential surface of hydrogen molecules adsorbed on graphane was computed. According to the calculations, hydrogen molecules are adsorbed on graphane in a perpendicular to the surface orientation with the minimum of the potential surface of around -3.6 kJ/mol located at the distance of 3.85 Å between the bond center of the hydrogen molecule and the mid-plane of graphane. The adsorption sites along the path from the downward-pointing carbon to the ring center of the graphane are energetically virtually equally preferable, which can enable nearly free translations of hydrogen molecules along these paths. Consequently, the hydrogen molecules on graphane most likely form a non-commensurate monolayer. The analysis of the remaining errors reveals a very high accuracy of the computed potential surface with an error bar of a few tenths of a kJ/mol. The obtained results are a high-precision benchmark for further theoretical and experimental studies of hydrogen molecules interacting with graphane.

  2. EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

    NASA Astrophysics Data System (ADS)

    Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

    2010-12-01

    Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals

  3. Biochemical Hydrogen Isotope Fractionation during Lipid Biosynthesis in Higher Plants

    NASA Astrophysics Data System (ADS)

    Kahmen, A.; Gamarra, B.; Cormier, M. A.

    2014-12-01

    Although hydrogen isotopes (δ2H) of leaf wax lipids are increasingly being applied as (paleo-) hydrological proxies, we still do not understand some of the basic processes that shape the δ2H values of these compounds. In general, it is believed that three variables shape the δ2H values of leaf wax lipids: source water δ2H values, evaporative deuterium (2H) enrichment of leaf water and the biosynthetic fractionation (ɛbio) during the synthesis of organic compounds. While the influences of source water δ2H values and leaf water evaporative 2H enrichment have been well documented, very little is known how ɛbio shapes the δ2H values of plant-derived lipids. I will present the results from recent experiments, where we show that the magnitude of ɛbio, and thus the δ2H value of plant-derived lipids, strongly depends on the carbon (C) metabolism of a plant. Specifically, I will show that plants that rely for their tissue formation on recently assimilated C have δ2H values in their n-alkanes that are up to 60‰ more negative than plants that depend for their tissue formation on stored carbohydrates. Our findings can be explained by the fact that NADPH is the primary source of hydrogen in plant lipids and that the δ2H value of NADPH differs whether NADPH was generated directly in the light reaction of photosynthesis or whether it was generated by processing stored carbohydrates. As such, the δ2H values of plant-derived lipids will directly depend on whether the tissue containing these lipids was synthesized using recent assimilates, e.g. in a C autonomous state or, if it was synthesized from stored or otherwise aquired C sources, e.g. in a not C autonomous state. Given the magnidude of this effect, our results have important implications for interpretation of plant-derived lipid δ2H values when used as (paleo-) hydrological proxies. In addition, our results suggest, that δ2H values of plant-derived lipids could be employed as a new tools to assess the C

  4. Iron isotope fractionation during microbial reduction of iron: The importance of adsorption

    NASA Astrophysics Data System (ADS)

    Icopini, G. A.; Anbar, A. D.; Ruebush, S. S.; Tien, M.; Brantley, S. L.

    2004-03-01

    In experiments investigating the causes of Fe isotope fractionation, the δ56/54Fe value of Fe(II) remaining in solution (Fe(II)(aq)) after reduction of Fe(III) (goethite) by Shewanella putrefaciens is ˜-1.2‰ relative to the goethite, in agreement with previous research. The addition of an electron shuttle did not affect fractionation, suggesting that Fe isotope fractionation may not be related to the kinetics of the electron transfer. Furthermore, in abiotic, anaerobic FeCl2(aq) experiments in which approximately one-third of Fe(II)(aq) is lost from solution due to adsorption of Fe(II) onto goethite, the δ56/54Fe value of Fe(II)(aq) remaining in solution is shifted by -0.8‰ relative to FeCl2. This finding demonstrates that anaerobic nonbiological interaction between Fe(II) and goethite can generate significant Fe isotope fractionation. Acid extraction of sorbed Fe(II) from goethite in experiments reveals that heavy Fe preferentially sorbs to goethite. Simple mass-balance modeling indicates that the isotopic composition of the sorbed Fe(II) pool is ˜+1.5‰ to +2.5‰ heavier than Fe in the goethite [˜2.7‰ 3.7‰ heavier than aqueous Fe(II)]. Mass balance is also consistent with a pool of heavy Fe that is not released to solution during acid extraction.

  5. Effects of hydrogen isotopes in the irradiation damage of CLAM steel

    NASA Astrophysics Data System (ADS)

    Zhao, M. Z.; Liu, P. P.; Zhu, Y. M.; Wan, F. R.; He, Z. B.; Zhan, Q.

    2015-11-01

    The isotope effect of hydrogen in irradiation damage plays an important role in the development of reduced activation Ferritic/Martensitic steels in nuclear reactors. The evolutions of microstructures and mechanical properties of China low active martensitic (CLAM) steel subjected to hydrogen and deuterium ions irradiation are studied comparatively. Under the same irradiation conditions, larger size and smaller density of dislocation loops are generated by deuterium ion than by hydrogen ion. Irradiation hardening occurs under the ion irradiation and the hardening induced by hydrogen ion is higher than by deuterium ion. Moreover, the coarsening of M23C6 precipitates is observed, which can be explained by the solute drag mechanisms. It turns out that the coarsening induced by deuterium ion irradiation is more distinct than by hydrogen ion irradiation. No distinct variations for the compositions of M23C6 precipitates are found by a large number of statistical data after hydrogen isotopes irradiation.

  6. Quest for Inexpensive Hydrogen Isotopic Fractionation: Do We Need 2D Quantum Confining in Porous Materials or Are Rough Surfaces Enough? The Case of Ammonia Nanoclusters.

    PubMed

    Mella, Massimo; Curotto, E

    2016-10-05

    We study the adsorption energetics and quantum properties of the molecular hydrogen isotopes H2, D2, and T2 onto the surface of rigid ammonia nanoclusters with quantum simulations and accurate model potential energy surfaces (PES). A highly efficient diffusion Monte Carlo (DMC) algorithm for rigid rotors allowed us to accurately define zero-point adsorption energies for the three isotopes, as well as the degree of translational and rotational delocalization that each affords on the surface. From the data emerges that the quantum adsorption energy (Eads) of T2 can be up to twice the one of H2 at 0 K, suggesting the possibility of exploiting some form of solid ammonia to selectivity separate hydrogen isotopes at low temperatures (≃20 K). This is discussed by focusing on the structural motif that may be more effective for the task. The analysis of the contributions to Eads, however, surprisingly indicates that the average kinetic energy (E(kin)) and rotation energy (Erot(kin)) of T2 can also be, respectively, 2 times and 20 times higher than those of H2; this finding markedly deviates from what is predicted for hydrogen molecules inside carbon nanotubes (CNT) or metallic-organic frameworks (MOF), where E(kin) and Erot(kin) is higher for H2 due to the unavoidable effects of confinement and hindrance to its rotational motion. The rationale for these differences is provided by the geometrical distributions for the rigid rotors, which reveal an increasingly stronger coupling between rotational and translational degrees of freedom upon increasing the isotopic mass. This effect has never been observed before on adsorbing surfaces (e.g., graphite) and is induced by a strongly anisotropic and anharmonic bowl-like potential experienced by the rotors.

  7. Hydrogen isotopic enrichment: an indicator of biodegradation at a petroleum hydrocarbon contaminated field site.

    PubMed

    Mancini, Silvia A; Lacrampe-Couloume, Georges; Jonker, Hendrikus; van Breukelen, Boris M; Groen, Jacobus; Volkering, Frank; Lollar, Barbara Sherwood

    2002-06-01

    Compound-specific carbon and hydrogen isotope analysis was used to investigate biodegradation of benzene and ethylbenzene in contaminated groundwater at Dow Benelux BV industrial site. delta13C values for dissolved benzene and ethylbenzene in downgradient samples were enriched by up to 2+/-0.5 per thousand, in 13C, compared to the delta13C value of the source area samples. delta2H values for dissolved benzene and ethylbenzene in downgradient samples exhibited larger isotopic enrichments of up to 27+/-5 per thousand for benzene and up to 50+/-5 per thousand for ethylbenzene relative to the source area. The observed carbon and hydrogen isotopic fractionation in downgradient samples provides evidence of biodegradation of both benzene and ethylbenzene within the study area at Dow Benelux BV. The estimated extents of biodegradation of benzene derived from carbon and hydrogen isotopic compositions for each sample are in agreement, supporting the conclusion that biodegradation is the primary control on the observed differences in carbon and hydrogen isotope values. Combined carbon and hydrogen isotope analyses provides the ability to compare biodegradation in the field based on two different parameters, and hence provides a stronger basis for assessment of biodegradation of petroleum hydrocarbon contaminants.

  8. Hydrogen Isotope Fractionation As a Tool to Identify Aerobic and Anaerobic PAH Biodegradation.

    PubMed

    Kümmel, Steffen; Starke, Robert; Chen, Gao; Musat, Florin; Richnow, Hans H; Vogt, Carsten

    2016-03-15

    Aerobic and anaerobic polycyclic aromatic hydrocarbon (PAH) biodegradation was characterized by compound specific stable isotope analysis (CSIA) of the carbon and hydrogen isotope effects of the enzymatic reactions initiating specific degradation pathways, using naphthalene and 2-methylnaphtalene as model compounds. Aerobic activation of naphthalene and 2-methylnaphthalene by Pseudomonas putida NCIB 9816 and Pseudomonas fluorescens ATCC 17483 containing naphthalene dioxygenases was associated with moderate carbon isotope fractionation (εC = -0.8 ± 0.1‰ to -1.6 ± 0.2‰). In contrast, anaerobic activation of naphthalene by a carboxylation-like mechanism by strain NaphS6 was linked to negligible carbon isotope fractionation (εC = -0.2 ± 0.2‰ to -0.4 ± 0.3‰). Notably, anaerobic activation of naphthalene by strain NaphS6 exhibited a normal hydrogen isotope fractionation (εH = -11 ± 2‰ to -47 ± 4‰), whereas an inverse hydrogen isotope fractionation was observed for the aerobic strains (εH = +15 ± 2‰ to +71 ± 6‰). Additionally, isotope fractionation of NaphS6 was determined in an overlaying hydrophobic carrier phase, resulting in more reliable enrichment factors compared to immobilizing the PAHs on the bottle walls without carrier phase. The observed differences especially in hydrogen fractionation might be used to differentiate between aerobic and anaerobic naphthalene and 2-methylnaphthalene biodegradation pathways at PAH-contaminated field sites.

  9. Strong Ionic Hydrogen Bonding Causes a Spectral Isotope Effect in Photoactive Yellow Protein

    PubMed Central

    Kaledhonkar, Sandip; Hara, Miwa; Stalcup, T. Page; Xie, Aihua; Hoff, Wouter D.

    2013-01-01

    Standard hydrogen bonds are of great importance for protein structure and function. Ionic hydrogen bonds often are significantly stronger than standard hydrogen bonds and exhibit unique properties, but their role in proteins is not well understood. We report that hydrogen/deuterium exchange causes a redshift in the visible absorbance spectrum of photoactive yellow protein (PYP). We expand the range of interpretable isotope effects by assigning this spectral isotope effect (SIE) to a functionally important hydrogen bond at the active site of PYP. The inverted sign and extent of this SIE is explained by the ionic nature and strength of this hydrogen bond. These results show the relevance of ionic hydrogen bonding for protein active sites, and reveal that the inverted SIE is a novel, to our knowledge, tool to probe ionic hydrogen bonds. Our results support a classification of hydrogen bonds that distinguishes the properties of ionic hydrogen bonds from those of both standard and low barrier hydrogen bonds, and show how this classification helps resolve a recent debate regarding active site hydrogen bonding in PYP. PMID:24314088

  10. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  11. Geometrical H/D isotope effect on hydrogen bonds in charged water clusters.

    PubMed

    Tachikawa, Masanori; Shiga, Motoyuki

    2005-08-31

    To investigate the proton/deuteron geometrical isotope effect of positively and negatively charged water complexes, H5O2+ and H3O2-, we have carried out accurate ab initio path integral simulations considering the electron correlation effect. It has been found that the isotope effect on the hydrogen bond is different between these two species in that the oxygen separation becomes shorter in H5O2+ while longer in H3O2- by deuteron substitution. This behavior is ascribed to the change in the quantum effect of hydrogen bonds whether the shared hydrogen is on a single or double well potential surface.

  12. Isotopic Studies of Hydrogen and Deuterium Phase IV at Multi-Megabar Pressures

    NASA Astrophysics Data System (ADS)

    Gregoryanz, Eugene; Guillaume, Christophe; Scheler, Thomas; Howie, Ross

    2013-06-01

    The recent discovery of the mixed atomic and molecular phase IV of hydrogen (deuterium) is exemplary of how the studies of hydrogen at multi-megabar pressures is constitutive to the understanding of simple systems at extreme compressions. Through a series of high pressure Raman spectroscopic experiments we have conducted an isotopic comparison between hydrogen and deuterium in phase I. Isotopic studies not only reveal differences in phase stability, imposing constraints on the P-T phase diagram, but also provide strong evidence for structural phenomena, such as proton (deuteron) tunnelling. New data will be presented over a wide temperature range.

  13. Design and synthesis of vanadium hydrazide gels for Kubas-type hydrogen adsorption: a new class of hydrogen storage materials.

    PubMed

    Hoang, Tuan K A; Webb, Michael I; Mai, Hung V; Hamaed, Ahmad; Walsby, Charles J; Trudeau, Michel; Antonelli, David M

    2010-08-25

    In this paper we demonstrate that the Kubas interaction, a nondissociative form of weak hydrogen chemisorption with binding enthalpies in the ideal 20-30 kJ/mol range for room-temperature hydrogen storage, can be exploited in the design of a new class of hydrogen storage materials which avoid the shortcomings of hydrides and physisorpion materials. This was accomplished through the synthesis of novel vanadium hydrazide gels that use low-coordinate V centers as the principal Kubas H(2) binding sites with only a negligible contribution from physisorption. Materials were synthesized at vanadium-to-hydrazine ratios of 4:3, 1:1, 1:1.5, and 1:2 and characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption, elemental analysis, infrared spectroscopy, and electron paramagnetic resonance spectroscopy. The material with the highest capacity possesses an excess reversible storage of 4.04 wt % at 77 K and 85 bar, corresponding to a true volumetric adsorption of 80 kg H(2)/m(3) and an excess volumetric adsorption of 60.01 kg/m(3). These values are in the range of the ultimate U.S. Department of Energy goal for volumetric density (70 kg/m(3)) as well as the best physisorption material studied to date (49 kg H(2)/m(3) for MOF-177). This material also displays a surprisingly high volumetric density of 23.2 kg H(2)/m(3) at room temperature and 85 bar--roughly 3 times higher than that of compressed gas and approaching the DOE 2010 goal of 28 kg H(2)/m(3). These materials possess linear isotherms and enthalpies that rise on coverage and have little or no kinetic barrier to adsorption or desorption. In a practical system these materials would use pressure instead of temperature as a toggle and can thus be used in compressed gas tanks, currently employed in many hydrogen test vehicles, to dramatically increase the amount of hydrogen stored and therefore the range of any vehicle.

  14. Density Functional Theory Study of Hydrogen Adsorption in a Ti-Decorated Mg-Based Metal-Organic Framework-74.

    PubMed

    Suksaengrat, Pitphichaya; Amornkitbamrung, Vittaya; Srepusharawoot, Pornjuk; Ahuja, Rajeev

    2016-03-16

    The Ti-binding energy and hydrogen adsorption energy of a Ti-decorated Mg-based metal-organic framework-74 (Mg-MOF-74) were evaluated by using first-principles calculations. Our results revealed that only three Ti adsorption sites were found to be stable. The adsorption site near the metal oxide unit is the most stable. To investigate the hydrogen-adsorption properties of Ti-functionalized Mg-MOF-74, the hydrogen-binding energy was determined. For the most stable Ti adsorption site, we found that the hydrogen adsorption energy ranged from 0.26 to 0.48 eV H2 (-1) . This is within the desirable range for practical hydrogen-storage applications. Moreover, the hydrogen capacity was determined by using ab initio molecular dynamics simulations. Our results revealed that the hydrogen uptake by Ti-decorated Mg-MOF-74 at temperatures of 77, 150, and 298 K and ambient pressure were 1.81, 1.74, and 1.29 H2  wt %, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. On the hydrogen adsorption and dissociation on Cu surfaces and nanorows

    NASA Astrophysics Data System (ADS)

    Álvarez-Falcón, Leny; Viñes, Francesc; Notario-Estévez, Almudena; Illas, Francesc

    2016-04-01

    Here we present a thorough density functional theory study, including and excluding dispersive forces interaction description, on the adsorption and dissociation of H2 molecule on the low-index Miller Cu (111), (100), and (110) surfaces and two different surface Cu nanorows, all displaying a different number of surface nearest neighbors, nn. The computational setup has been optimized granting an accuracy below 0.04 eV. Surface and nanorow energies-for which a new methodology to extract them is presented- are found to follow the nn number. However, the adsorption strength is found not to. Thus, the adsorption energies seem to be governed by a particular orbital ↔ band interaction rather than by the simple nn surface saturation. The van der Waals (vdW) forces are found to play a key role in the adsorption of H2, and merely an energetic adjustment on chemisorbed H adatoms. Neither clear trends are observed for H2 and H adsorption energies, and H2 dissociation energy with respect nn, and nor Brønsted-Evans-Polanyi, making H2 adsorption and dissociation a trend outlier compared to other cases. H2 is found to adsorb and dissociate on Cu(100) surface. On the Cu(111) surface, the rather small H2 adsorption energy would prevent H2 dissociation, regardless if it is thermodynamically driven. On Cu(110) surface, the H2 dissociation process would be endothermic and achievable if adsorption energy is released on surpassing the dissociation energy barrier. On low-coordinated sites on Cu nanorows, vdW plays a key role in the H2 dissociation process, which otherwise is found to be endothermic. Indeed, dispersive forces turn the process markedly exothermic. Nanoparticle Cu systems must display Cu(100) surfaces or facets in order to dissociate H2, vital in many hydrogenation processes.

  16. FTIR spectroscopic and computational studies on hydrogen adsorption on the zeolite Li-FER.

    PubMed

    Nachtigall, P; Garrone, E; Palomino, G Turnes; Delgado, M Rodríguez; Nachtigallová, D; Areán, C Otero

    2006-05-21

    The interaction, at a low temperature, between molecular hydrogen and the zeolite Li-FER was studied by means of variable temperature infrared spectroscopy and theoretical calculations using a periodic DFT model. The adsorbed dihydrogen molecule becomes infrared active, giving a characteristic IR absorption band (H-H stretching) at 4090 cm(-1). Three different Li(+) site types with respect to H(2) adsorption were found in the zeolite, two of which adsorb H(2). Calculations showed a similar interaction energy for these two sites, which was found to agree with the experimentally determined value of standard adsorption enthalpy of DeltaH(0) = -4.1 (+/-0.8) kJ mol(-1). The results are discussed in the broader context of previously reported data for H(2) adsorption on Na-FER and K-FER.

  17. Insights into hydrogen atom adsorption on and the electrochemical properties of nitrogen-substituted carbon materials.

    PubMed

    Zhu, Z H; Hatori, H; Wang, S B; Lu, G Q

    2005-09-08

    The nitrogen substitution in carbon materials is investigated theoretically using the density functional theory method. Our calculations show that nitrogen substitution decreases the hydrogen adsorption energy if hydrogen atoms are adsorbed on both nitrogen atoms and the neighboring carbon atoms. On the contrary, the hydrogen adsorption energy can be increased if hydrogen atoms are adsorbed only on the neighboring carbon atoms. The reason can be explained by the electronic structures analysis of N-substituted graphene sheets. Nitrogen substitution reduces the pi electron conjugation and increases the HOMO energy of a graphene sheet, and the nitrogen atom is not stable due to its 3-valent character. This raises an interesting research topic on the optimization of the N-substitution degree, and is important to many applications such as hydrogen storage and the tokamaks device. The electronic structure studies also explain well why nitrogen substitution increases the capacitance but decreases the electron conductivity of carbon electrodes as was experimentally observed in our experiments on the supercapacitor.

  18. Molecular Paleohydrology: Interpreting the Hydrogen-Isotopic Composition of Lipid Biomarkers from Photosynthesizing Organisms

    NASA Astrophysics Data System (ADS)

    Sachse, Dirk; Billault, Isabelle; Bowen, Gabriel J.; Chikaraishi, Yoshito; Dawson, Todd E.; Feakins, Sarah J.; Freeman, Katherine H.; Magill, Clayton R.; McInerney, Francesca A.; van der Meer, Marcel T. J.; Polissar, Pratigya; Robins, Richard J.; Sachs, Julian P.; Schmidt, Hanns-Ludwig; Sessions, Alex L.; White, James W. C.; West, Jason B.; Kahmen, Ansgar

    2012-05-01

    Hydrogen-isotopic abundances of lipid biomarkers are emerging as important proxies in the study of ancient environments and ecosystems. A decade ago, pioneering studies made use of new analytical methods and demonstrated that the hydrogen-isotopic composition of individual lipids from aquatic and terrestrial organisms can be related to the composition of their growth (i.e., environmental) water. Subsequently, compound-specific deuterium/hydrogen (D/H) ratios of sedimentary biomarkers have been increasingly used as paleohydrological proxies over a range of geological timescales. Isotopic fractionation observed between hydrogen in environmental water and hydrogen in lipids, however, is sensitive to biochemical, physiological, and environmental influences on the composition of hydrogen available for biosynthesis in cells. Here we review the factors and processes that are known to influence the hydrogen-isotopic compositions of lipids—especially n-alkanes—from photosynthesizing organisms, and we provide a framework for interpreting their D/H ratios from ancient sediments and identify future research opportunities.

  19. Multiscale Study of Hydrogen Adsorption on Six Designed Covalent Organic Frameworks Based on Porphyrazine, Cyclobutane and Scandium

    NASA Astrophysics Data System (ADS)

    Li, Le-Le; Gao, Teng-Fei; Zhang, Ruan-Yu; Zhang, Hong

    2014-09-01

    The first-principles method of hydrogen adsorption is used to investigate the interaction of H2 with the scandium-porphyrazine (Sc-Pz) and porphyrazine (Pz) clusters. The result shows that the interaction of H2 with Sc-Pz is stronger than with Pz. Then grand canonical Monte Carlo simulations are used to investigate hydrogen adsorption in six designed covalent organic frameworks (COFs), which are designed based on porphyrazine, cyclobutane and scandium. When the pressure is from 0.1 to 100 bar and the temperature is 298 K and 77 K, the hydrogen adsorption capacities of the six COFs are calculated. We further study the importance of Sc and fillers to improve the H2 uptake in the modified COFs by analyzing the isosteric heat of hydrogen adsorption.

  20. Hydrogen adsorption-mediated synthesis of concave Pt nanocubes and their enhanced electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lu, Bang-An; Du, Jia-Huan; Sheng, Tian; Tian, Na; Xiao, Jing; Liu, Li; Xu, Bin-Bin; Zhou, Zhi-You; Sun, Shi-Gang

    2016-06-01

    Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts.Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts. Electronic supplementary information (ESI) available: Details of DFT calculation, SEM images of concave Pt nanocubes, mass activity and stability characterization of the catalysts. See DOI: 10.1039/c6nr02349e

  1. HYDROGEN ADSORPTION ON β-TiAl (001) AND Ni/TiAl (001) SURFACES

    NASA Astrophysics Data System (ADS)

    Mubarak, A. A. Karim; Alelaimi, Mahmoud

    2014-04-01

    In this paper, we present first principles calculations of the energetic, electronic and magnetic properties of the variant termination of TiAl (001) and Ni/TiAl (001) surfaces with and without hydrogen atoms. The calculations have been performed within the density functional theory using full-potential linearized augmented plane wave method. The generalized gradient approximation (GGA) is utilized as the exchange-correlation energy. The octahedral site is the stable absorption site of H atom in the β-TiAl system. This absorption reduces the cohesive energy of β-TiAl system due to increase in the lattice constant. The surface energy for both TiAl (001) terminations is calculated. The stable adsorption site of H atoms on the variant termination of TiAl (001) surface is performed. The adsorption energy of hydrogen on Ti is more energetic than that on Al. The adsorption of H atom on both terminations of H/Ni/TiAl (001) is more preferable at the bridge site. The adsorption energies are enhanced on Ni atom due to the contraction between d-Ni bands and TiAl substrate band.

  2. NMR studies of solid pentachlorophenol-4-methylpyridine complexes exhibiting strong OHN hydrogen bonds: geometric H/D isotope effects and hydrogen bond coupling cause isotopic polymorphism.

    PubMed

    Ip, Brenda C K; Shenderovich, Ilya G; Tolstoy, Peter M; Frydel, Jaroslaw; Denisov, Gleb S; Buntkowsky, Gerd; Limbach, Hans-Heinrich

    2012-11-26

    We have studied the hydrogen bond interactions of (15)N labeled 4-methylpyridine (4-MP) with pentachlorophenol (PCP) in the solid state and in polar solution using various NMR techniques. Previous spectroscopic, X-ray, and neutron crystallographic studies showed that the triclinic 1:1 complex (4-MPPCP) exhibits the strongest known intermolecular OHN hydrogen bond in the solid state. By contrast, deuteration of the hydrogen bond gives rise to the formation of a monoclinic structure exhibiting a weaker hydrogen bond. By performing NMR experiments at different deuterium fractions and taking advantage of dipolar (1)H-(15)N recoupling under combined fast MAS and (1)H decoupling, we provide an explanation of the origin of the isotopic polymorphism of 4-MPPCP and improve previous chemical shift correlations for OHN hydrogen bonds. Because of anharmonic ground state vibrations, an ODN hydrogen bond in the triclinic form exhibits a shorter oxygen-hydron and a longer oxygen-nitrogen distance as compared to surrounding OHN hydrogen bonds, which also implies a reduction of the local dipole moment. The dipole-dipole interaction between adjacent coupled OHN hydrogen bonds which determines the structure of triclinic 4-MPPCP is then reduced by deuteration, and other interactions become dominant, leading to the monoclinic form. Finally, the observation of stronger OHN hydrogen bonds by (1)H NMR in polar solution as compared to the solid state is discussed.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Strategies for increasing hydrogen storage capacity and adsorption energy in MOFs

    NASA Astrophysics Data System (ADS)

    Yaghi, Omar

    2007-03-01

    Storage of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressures as a gas or very low temperatures as a liquid. Worldwide effort is focused on storage of hydrogen with sufficient efficiency to allow its use in stationary and mobile fueling applications. DOE has set performance targets for on-board automobile storage systems to have densities of 60 mg H2/g (gravimetric) and 45 g H2/L (volumetric) for year 2010. These are system goals. Metal-organic frameworks (MOFs) have recently been identified as promising adsorbents (physisorption) for H2 storage, although little data are available for their adsorption behavior at saturation: a critical parameter for gauging the practicality of any material. This presentation will report adsorption data collected for seven MOF materials at 77 K which leads to saturation at pressures between 25 and 80 bar with uptakes from 2% to 7.5%. Strategies for increasing the adsorption energy of hydrogen in MOFs will also be presented.

  5. Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

    SciTech Connect

    Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Hupalo, Myron; Wang, Yangang; McDougall, Dan; Tringides, Michael; Ho, Kaiming

    2013-12-14

    The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H{sub 2} molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H{sub 2} molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

  6. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption

    NASA Astrophysics Data System (ADS)

    Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao; Subbaraman, Ram; Danilovic, Nemanja; van der Vliet, Dennis; Paulikas, Arvydas P.; Stamenkovic, Vojislav R.; Markovic, Nenad M.

    2013-04-01

    The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt0.1Ru0.9) with an optimal balance between the active sites that are required for the adsorption/dissociation of H2 and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

  7. How hydroxylation affects hydrogen adsorption and formation on nanosilicates

    NASA Astrophysics Data System (ADS)

    Kerkeni, Boutheïna; Bacchus-Montabonel, Marie-Christine; Bromley, Stefan T.

    2017-06-01

    Silicate dust constitutes one of the primary solid components of the Universe and is thought to be an essential enabler for complex chemistry in a number of astronomical environments. Hydroxylated silicate nanoclusters (MgO)x(SiO2)y(H2O)z, where strongly absorbed water molecules are dissociated on the silicate surface, are likely to be persistent in diffuse clouds. Such precursor species are thus also primary candidates as seeds for the formation and growth of icy dust grains in dense molecular clouds. Using density functional calculations we investigate the reactivity of hydroxylated pyroxene nanoclusters (Mg4Si4O12)(H2O)N (N = 1-4) towards hydrogen physisorption, chemisorption and H2 formation. Our results show that increased hydroxylation leads to a significant reduction in the energy range for the physisorption and chemisorption of single H atoms, when compared to bare silicate grains and bare bulk silicate surfaces. Subsequent chemisorption of a second H atom is, however, little affected by hydroxylation. The H2 reaction barrier for the recombination of two chemisorbed H atoms tends to follow a linear correlation with respect to the 2Hchem binding energy, suggestive of a general Brønsted-Evans-Polanyi relation for H2 formation on silicate grains, independent of dust grain size, composition and degree of hydroxylation.

  8. Surface and subsurface hydrogen: adsorption properties on transition metals and near-surface alloys.

    PubMed

    Greeley, Jeff; Mavrikakis, Manos

    2005-03-03

    Periodic, self-consistent DFT-GGA calculations are used to study the thermochemical properties of both surface and subsurface atomic hydrogen on a variety of pure metals and near-surface alloys (NSAs). For surface hydrogen on pure metals, calculated site preferences, adsorption geometries, vibrational frequencies, and binding energies are reported and are found to be in good agreement with available experimental data. On NSAs, defined as alloys wherein a solute is present near the surface of a host metal in a composition different from the bulk composition, surface hydrogen generally binds more weakly than it binds to the pure-metal components composing the alloys. Some of the NSAs even possess the unusual property of binding hydrogen as weakly as the noble metals while, at the same time, dissociating H(2) much more easily. On both NSAs and pure metals, formation of surface hydrogen is generally exothermic with respect to H(2)(g). In contrast, formation of subsurface hydrogen is typically endothermic with respect to gas-phase H(2) (the only exception to this general statement is found for pure Pd). As with surface H, subsurface H typically binds more weakly to NSAs than to the corresponding pure-metal components of the alloys. The diffusion barrier for hydrogen from surface to subsurface sites, however, is usually lower on NSAs compared to the pure-metal components, suggesting that population of subsurface sites may occur more rapidly on NSAs.

  9. Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

    SciTech Connect

    Li, Ming; Kang, Zhan; Huang, Xiaobo

    2015-08-28

    Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

  10. Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Li, Ming; Huang, Xiaobo; Kang, Zhan

    2015-08-01

    Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

  11. American woodcock migratory connectivity as indicated by hydrogen isotopes

    USGS Publications Warehouse

    Sullins, Daniel S.; Conway, Warren C.; Haukos, David A.; Hobson, Keith A.; Wassenaar, Leonard I; Comer, Christopher E.; Hung, I-Kuai

    2016-01-01

    To identify factors contributing to the long-term decline of American woodcock, a holistic understanding of range-wide population connectivity throughout the annual cycle is needed. We used band recovery data and isotopic composition of primary (P1) and secondary (S13) feathers to estimate population sources and connectivity among natal, early fall, and winter ranges of hunter-harvested juvenile American woodcock. We used P1 feathers from known-origin pre-fledged woodcock (n = 43) to create a hydrogenδ2Hf isoscape by regressing δ2Hf against expected growing-season precipitation (δ2Hp). Modeled δ2Hp values explained 79% of the variance in P1 δ2Hf values, indicating good model fit for estimating woodcock natal origins. However, a poor relationship (r2 = 0.23) between known-origin, S13 δ2Hf values, and expected δ2Hp values precluded assignment of early fall origins. We applied the δ2Hfisoscape to assign natal origins using P1 feathers from 494 hunter-harvested juvenile woodcock in the United States and Canada during 2010–2011 and 2011–2012 hunting seasons. Overall, 64% of all woodcock origins were assigned to the northernmost (>44°N) portion of both the Central and Eastern Management Regions. In the Eastern Region, assignments were more uniformly distributed along the Atlantic coast, whereas in the Central Region, most woodcock were assigned to origins within and north of the Great Lakes region. We compared our origin assignments to spatial coverage of the annual American woodcock Singing Ground Survey (SGS) and evaluated whether the survey effectively encompasses the entire breeding range. When we removed the inadequately surveyed Softwood shield Bird Conservation Region (BCR) from the northern portion of the SGS area, only 48% of juvenile woodcock originated in areas currently surveyed by the SGS. Of the individuals assigned to the northernmost portions of the breeding range, several were harvested in the southern extent of the

  12. Adsorption and migration behavior of Si atoms on the hydrogen-terminated diamond (001) surface: A first principles study

    NASA Astrophysics Data System (ADS)

    Liu, Xuejie; Qiao, Haimao; Kang, Congjie; Ren, Yuan; Tan, Xin; Sun, Shiyang

    2017-10-01

    The adsorption and migration activation energies of a silicon (Si) atom on a hydrogen-terminated diamond (001) surface were calculated using first principles methods based on density functional theory. On the fully hydrogen-terminated surface, the surface carbon atoms possess saturated bonds. The Si atom cannot bond with the surface carbon atoms; thus, the adsorption energy of the Si atom is low. However, on the hydrogen-terminated surface with one or two open radical sites (ORS), the adsorption energy of a Si atom increases to 3.1 eV and even up to 4.7 eV, thereby forming a stable configuration. Along the three ORS in the direction of dimer row or chain, a Si atom can migrate between two deep basins with migration activation energies at 1.5 or 1.3 eV. Given the relatively large energy barrier at approximately 3.8 or 4.7 eV, escaping from the deep basin is difficult for the Si atom. This investigation showed that the number and distribution of ORS, namely, the adsorption site of hydrogen atoms and the removal site of surface hydrogen atoms, can affect the adsorption and migration of Si atoms on the hydrogen-terminated diamond surface. Electron structure analysis further reveals that the reactivity of the surface C atoms and the charge transfer amount between the Si and surface C atoms affect the adsorption and migration of Si atoms.

  13. Hydrogen isotope fractionation by Methanothermobacter thermoautotrophicus in coculture and pure culture conditions

    NASA Astrophysics Data System (ADS)

    Yoshioka, Hideyoshi; Sakata, Susumu; Kamagata, Yoichi

    2008-06-01

    We grew a hydrogen-utilizing methanogen, Methanothermobacter thermoautotrophicus strain ΔH, in coculture and pure culture conditions to evaluate the hydrogen isotope fractionation associated with carbonate reduction under low (< several tens of μM; coculture) and high (>6 mM; pure culture) concentrations of H 2 in the headspace. In the cocultures, which were grown at 55 °C with a thermophilic butyrate-oxidizing syntroph, the hydrogen isotopic relationship between methane and water was well represented by the following equation: δD=0.725(±0.003)·δDO-275(±3), in which the hydrogen isotope fractionation factor ( αH) was 0.725 ± 0.003. The relationship was consistent with the isotopic data on methane and water from terrestrial fields (a peat bog in Washington State, USA, and a sandy aquifer in Denmark), where carbonate reduction was reported to be the dominant pathway of methanogenesis. In the pure cultures, grown at 55 and 65 °C, the αH values were 0.755 ± 0.014 and 0.749 ± 0.014, respectively. Dependence of αH on growth temperature was not observed. The αH value at 55 °C in the pure culture was slightly higher than that in the coculture, a finding that disagrees with a hypothesis proposed by Burke [Burke, Jr. R. A. (1993) Possible influence of hydrogen concentration on microbial methane stable hydrogen isotopic composition. Chemosphere26, 55-67] that hydrogen isotope fractionation between methane and water increases (and αH decreases) with increasing H 2 concentration.

  14. Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

    NASA Astrophysics Data System (ADS)

    Brown, Craig M.; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K.; Kepert, Cameron J.

    2009-05-01

    Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

  15. Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study.

    PubMed

    Brown, Craig M; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K; Kepert, Cameron J

    2009-05-20

    Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

  16. New Carbon-Based Porous Materials with Increased Heats of Adsorption for Hydrogen Storage

    SciTech Connect

    Snurr, Randall Q.; Hupp, Joseph T.; Kanatzidis, Mercouri G.; Nguyen, SonBinh T.

    2014-11-03

    . Only after modeling suggested record-breaking hydrogen uptake at 77 K did we proceed to synthesize, characterize, and test the material, ultimately yielding experimental results that agreed closely with predictions that were made before the material was synthesized. We also synthesized, characterized, and computationally simulated the behavior of two new materials displaying the highest experimental Brunauer$-$Emmett$-$Teller (BET) surface areas of any porous materials reported to date (~7000 m2/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, was the use of a supercritical CO2 activation technique developed by our team. In our efforts to increase the hydrogen binding energy, we developed the first examples of “zwitterionic” metal-organic frameworks (MOFs). The two structures feature zwitterionic characteristics arising from N-heterocyclic azolium groups in the linkers and negatively charged Zn2(CO2)5 nodes. These groups interact strongly with the H2 quadrupole. High initial isosteric heats of adsorption for hydrogen were measured at low H2 loading. Simulations were used to determine the H2 binding sites, and results were compared with inelastic neutron scattering. In addition to MOFs, the project produced a variety of related materials known as porous organic frameworks (POFs), including robust catechol-functionalized POFs with tunable porosities and degrees of functionalization. Post-synthesis metalation was readily carried out with a wide range of metal precursors (CuII, MgII, and MnII salts and complexes), resulting in metalated POFs with enhanced heats of hydrogen adsorption compared to the starting nonmetalated materials. Isosteric heats of adsorption as high as 9.6 kJ/mol were observed, compared to typical values around 5 kJ/mol in unfunctionalized MOFs and POFs

  17. Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nowak-Lovato, K.

    2014-12-01

    Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

  18. Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

    NASA Technical Reports Server (NTRS)

    Tyburczy, James A.; Krishnamurthy, R. V.; Epstein, Samuel; Ahrens, Thomas J.

    1988-01-01

    Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

  19. Thermal management of the adsorption-based vessel for hydrogeneous gas storage

    NASA Astrophysics Data System (ADS)

    Vasiliev, L. L.; Kanonchik, L. E.; Babenko, V. A.

    2012-09-01

    Thermal management is a design bottleneck in the creation of rational gas storage sorption systems. Inefficient heat transfer in a sorption bed is connected with a relatively low thermal conductivity (0.1-0.5 W/(mṡK)) and an appreciable sorption heat of activated gas storage materials. This work is devoted to the development of a thermally regulated onboard system of hydrogenous gas (methane and hydrogen) storage with the use of novel carbon sorbents. A hydrogenous gas storage system based on combined gas adsorption and compression at moderate pressures (3-6 MPa) and low temperatures (from the temperature of liquid nitrogen of about 77 K to a temperature of 273 K) is suggested.

  20. Adsorption and diffusion characteristics of lithium on hydrogenated α- and β-silicene

    PubMed Central

    Kandemir, Ali; Bacaksiz, Cihan

    2017-01-01

    Using first-principles density functional theory calculations, we investigate adsorption properties and the diffusion mechanism of a Li atom on hydrogenated single-layer α- and β-silicene on a Ag(111) surface. It is found that a Li atom binds strongly on the surfaces of both α- and β-silicene, and it forms an ionic bond through the transfer of charge from the adsorbed atom to the surface. The binding energies of a Li atom on these surfaces are very similar. However, the diffusion barrier of a Li atom on H-α-Si is much higher than that on H-β-Si. The energy surface calculations show that a Li atom does not prefer to bind in the vicinity of the hydrogenated upper-Si atoms. Strong interaction between Li atoms and hydrogenated silicene phases and low diffusion barriers show that α- and β-silicene are promising platforms for Li-storage applications. PMID:28904835

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

    SciTech Connect

    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; 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.

  2. Measurements of Cosmic-Ray Hydrogen and Helium Isotopes with the PAMELA Experiment

    NASA Astrophysics Data System (ADS)

    Adriani, O.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Boezio, M.; Bogomolov, E. A.; Bongi, M.; Bonvicini, V.; Bottai, S.; Bruno, A.; Cafagna, F.; Campana, D.; Carlson, P.; Casolino, M.; Castellini, G.; De Donato, C.; De Santis, C.; De Simone, N.; Di Felice, V.; Formato, V.; Galper, A. M.; Karelin, A. V.; Koldashov, S. V.; Koldobskiy, S.; Krutkov, S. Y.; Kvashnin, A. N.; Leonov, A.; Malakhov, V.; Marcelli, L.; Martucci, M.; Mayorov, A. G.; Menn, W.; Mergè, M.; Mikhailov, V. V.; Mocchiutti, E.; Monaco, A.; Mori, N.; Munini, R.; Osteria, G.; Palma, F.; Panico, B.; Papini, P.; Pearce, M.; Picozza, P.; Ricci, M.; Ricciarini, S. B.; Sarkar, R.; Scotti, V.; Simon, M.; Sparvoli, R.; Spillantini, P.; Stozhkov, Y. I.; Vacchi, A.; Vannuccini, E.; Vasilyev, G.; Voronov, S. A.; Yurkin, Y. T.; Zampa, G.; Zampa, N.

    2016-02-01

    The cosmic-ray hydrogen and helium (1H, 2H, 3He, 4He) 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 2H and 3He 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. Carbon and hydrogen isotopic composition of bacterial methane in a shallow freshwater lake

    SciTech Connect

    Woltemate, I.; Whiticar, M.J.; Schoell, M.

    1984-09-01

    Anoxic sediments from freshwater environments such as bogs, swamps, and lakes undergoing early diagenesis are frequently characterized by the formation of biogenic methane. Freshwater biogenic methanes exhibit carbon and hydrogen isotopic values strongly depleted in C-13 and deuterium relative to the respective values for carbon dioxide and formation water. The percentages of methane generated by fermentation and carbon dioxide reduction can be estimated by comparison of hydrogen isotopes in the formation water and methane. On the basis of these hydrogen isotope data, about 75% of the methane formation in Wurmsee comes from acetate reduction. Fermentation is thus the dominant although not exclusive process. Carbon dioxide reduction contributed the balance of the bacterial methane generated. 35 references, 5 figures, 1 table.

  4. A Biomimetic Approach to New Adsorptive Hydrogen Storage Metal-Organic Frameworks

    SciTech Connect

    Zhou, Hongcai J

    2015-08-12

    In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storage goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the

  5. Plant leaf wax biomarkers capture gradients in hydrogen isotopes of precipitation from the Andes and Amazon

    NASA Astrophysics Data System (ADS)

    Feakins, Sarah J.; Bentley, Lisa Patrick; Salinas, Norma; Shenkin, Alexander; Blonder, Benjamin; Goldsmith, Gregory R.; Ponton, Camilo; Arvin, Lindsay J.; Wu, Mong Sin; Peters, Tom; West, A. Joshua; Martin, Roberta E.; Enquist, Brian J.; Asner, Gregory P.; Malhi, Yadvinder

    2016-06-01

    Plant leaf waxes have been found to record the hydrogen isotopic composition of precipitation and are thus used to reconstruct past climate. To assess how faithfully they record hydrological signals, we characterize leaf wax hydrogen isotopic compositions in forest canopy trees across a highly biodiverse, 3 km elevation range on the eastern flank of the Andes. We sampled the dominant tree species and assessed their relative abundance in the tree community. For each tree we collected xylem and leaf samples for analysis of plant water and plant leaf wax hydrogen isotopic compositions. In total, 176 individuals were sampled across 32 species and 5 forest plots that span the gradient. We find both xylem water and leaf wax δD values of individuals correlate (R2 = 0.8 and R2 = 0.3 respectively) with the isotopic composition of precipitation (with an elevation gradient of -21‰ km-1). Minimal leaf water enrichment means that leaf waxes are straightforward recorders of the isotopic composition of precipitation in wet climates. For these tropical forests we find the average fractionation between source water and leaf wax for C29n-alkanes, -129 ± 2‰ (s.e.m., n = 136), to be indistinguishable from that of temperate moist forests. For C28n-alkanoic acids the average fractionation is -121 ± 3‰ (s.e.m., n = 102). Sampling guided by community assembly within forest plots shows that integrated plant leaf wax hydrogen isotopic compositions faithfully record the gradient of isotopes in precipitation with elevation (R2 = 0.97 for n-alkanes and 0.60 for n-alkanoic acids). This calibration study supports the use of leaf waxes as recorders of the isotopic composition of precipitation in lowland tropical rainforest, tropical montane cloud forests and their sedimentary archives.

  6. The adsorption and desorption of hydrogen and carbon monoxide on bimetallic RePt(111) surfaces

    NASA Astrophysics Data System (ADS)

    Godbey, David J.; Somorjai, G. A.

    1988-10-01

    Bimetallic surfaces of rhenium on Pt(111) were prepared by vapor depositing rhenium on Pt(111). The adsorption and desorption behavior of CO and H 2 on bimetallic PtRe surfaces were studied using temperature programmed desorption, and compared to the behavior of CO and H 2 on the monometallic Pt(111) and Re(0001) counterparts. Depositing rhenium on a Pt(111) surface decreased the activation energy of desorption of hydrogen, and a surface composed of 0.37 monolayers of rhenium on Pt(111) showed an activation energy of hydrogen desorption that was 2.5 {kcal}/{mol} less than the 19 {kcal}/{mol} displayed by the monometallic Pt(111) surface. In contrast, the activation energy of desorption of CO from bimetallic surfaces depended very little on the bimetallic surface composition, and a value of 27 {kcal}/{mol} was observed for low CO coverages. At saturation exposures of both H 2 and CO, maximum adsorption capacities were obtained for bimetallic surfaces. A surface composed of 0.2 monolayers of rhenium on Pt(111) adsorbed 20% more hydrogen than did Pt(111) alone, while a surface composed of 0.3 monolayers of rhenium on Pt(111) adsorbed 40% more CO than did Pt(111) alone. The results obtained show that surfaces exposing both rhenium and platinum atoms show adsorption/desorption behavior towards hydrogen and CO that is different than the behavior shown by either monometallic platinum or rhenium surfaces. Since the chemisorption behavior cannot be explained as a simple combination of the two metallic components of the surface, it is concluded that an electronic interaction between the two metals at the platinum-rhenium interface modifies the bonding of adsorbates at the mixed metal sites.

  7. Adsorption as a cause for iron isotope fractionation in reduced groundwater

    NASA Astrophysics Data System (ADS)

    Teutsch, Nadya; von Gunten, Urs; Porcelli, Don; Cirpka, Olaf A.; Halliday, Alex N.

    2005-09-01

    Iron isotopes were used to investigate iron transformation processes during an in situ field experiment for removal of dissolved Fe from reduced groundwater. This experiment provided a unique setting for exploring Fe isotope fractionation in a natural system. Oxygen-containing water was injected at a test well into an aquifer containing Fe(II)-rich reduced water, leading to oxidation of Fe(II) and precipitation of Fe(III)(hydr)oxides. Subsequently, groundwater was extracted from the same well over a time period much longer than the injection time. Since the surrounding water is rich in Fe(II), the Fe(II) concentration in the extracted water increased over time. The increase was strongly retarded in comparison to a conservative tracer added to the injected solution, indicating that adsorption of Fe(II) onto the newly formed Fe(III)(hydr)oxides occurred. A series of injection-extraction (push-pull) cycles were performed at the same well. The δ 57Fe/ 54Fe of pre-experiment background groundwater (-0.57 ± 0.17 ‰) was lighter than the sediment leach of Fe(III) (-0.24 ± 0.08 ‰), probably due to slight fractionation (only ˜0.3 ‰) during microbial mediated reductive dissolution of Fe(III)(hydr)oxides present in the aquifer. During the experiment, Fe(II) was adsorbed from native groundwater drawn into the oxidized zone and onto Fe(III)(hydr)oxides producing a very light groundwater component with δ 57Fe/ 54Fe as low as -4 ‰, indicating that heavier Fe(II) is preferentially adsorbed to the newly formed Fe(III)(hydr)oxides surfaces. Iron concentrations increased with time of extraction, and δ 57Fe/ 54Fe linearly correlated with Fe concentrations (R 2 = 0.95). This pattern was reproducible over five individual cycles, indicating that the same process occurs during repeated injection/extraction cycles. We present a reactive transport model to explain the observed abiotic fractionation due to adsorption of Fe(II) on Fe(III)(hydr)oxides. The fractionation is

  8. Hydrogen isotopic compositions of n-alkanes from terrestrial plants correlate with their ecological life forms.

    PubMed

    Liu, Weiguo; Yang, Hong; Li, Liwu

    2006-11-01

    Stable hydrogen isotopic compositions (deltaD) of compound-specific biomarkers, such as n-alkanes from plant leaf waxes, can be used as a proxy for paleoclimatic change. However, the relationship between hydrogen isotopes of plant leaf wax and plant ecological life forms is not well understood. Here, we report the deltaD of n-alkanes from 34 modern terrestrial plants, including twenty-one C(3) plants and thirteen C(4) plants from northwestern China, determined using gas chromatography/thermal conversion/isotope ratio mass spectrometry. Our data show that the stable hydrogen isotopes are poorly correlated with the plant photosynthetic pathway (C(3) vs. C(4)) and that they do not give clear regional precipitation signals. Together with a comparative analysis of published deltaD values from plant leaf waxes in other regions, we believe that the stable hydrogen isotope of plant leaf waxes is more closely related to ecological life forms of these terrestrial plants (i.e. tree, shrub, and grass). In general, the grasses have more negative deltaD values than the co-occurring trees and shrubs. Our findings suggest that the deltaD values of sedimentary leaf waxes from higher plants may record changes of a plant ecosystem under the influence of environmental alteration and imply that reconstruction of the paleoclimate using deltaD values from plant n-alkanes should be based upon specific plant taxa, and comparison should be made among plants with similar ecological life forms.

  9. Major evolutionary trends in hydrogen isotope fractionation of vascular plant leaf waxes.

    PubMed

    Gao, Li; Edwards, Erika J; Zeng, Yongbo; Huang, Yongsong

    2014-01-01

    Hydrogen isotopic ratios of terrestrial plant leaf waxes (δD) have been widely used for paleoclimate reconstructions. However, underlying controls for the observed large variations in leaf wax δD values in different terrestrial vascular plants are still poorly understood, hampering quantitative paleoclimate interpretation. Here we report plant leaf wax and source water δD values from 102 plant species grown in a common environment (New York Botanic Garden), chosen to represent all the major lineages of terrestrial vascular plants and multiple origins of common plant growth forms. We found that leaf wax hydrogen isotope fractionation relative to plant source water is best explained by membership in particular lineages, rather than by growth forms as previously suggested. Monocots, and in particular one clade of grasses, display consistently greater hydrogen isotopic fractionation than all other vascular plants, whereas lycopods, representing the earlier-diverging vascular plant lineage, display the smallest fractionation. Data from greenhouse experiments and field samples suggest that the changing leaf wax hydrogen isotopic fractionation in different terrestrial vascular plants may be related to different strategies in allocating photosynthetic substrates for metabolic and biosynthetic functions, and potential leaf water isotopic differences.

  10. Major Evolutionary Trends in Hydrogen Isotope Fractionation of Vascular Plant Leaf Waxes

    PubMed Central

    Gao, Li; Edwards, Erika J.; Zeng, Yongbo; Huang, Yongsong

    2014-01-01

    Hydrogen isotopic ratios of terrestrial plant leaf waxes (δD) have been widely used for paleoclimate reconstructions. However, underlying controls for the observed large variations in leaf wax δD values in different terrestrial vascular plants are still poorly understood, hampering quantitative paleoclimate interpretation. Here we report plant leaf wax and source water δD values from 102 plant species grown in a common environment (New York Botanic Garden), chosen to represent all the major lineages of terrestrial vascular plants and multiple origins of common plant growth forms. We found that leaf wax hydrogen isotope fractionation relative to plant source water is best explained by membership in particular lineages, rather than by growth forms as previously suggested. Monocots, and in particular one clade of grasses, display consistently greater hydrogen isotopic fractionation than all other vascular plants, whereas lycopods, representing the earlier-diverging vascular plant lineage, display the smallest fractionation. Data from greenhouse experiments and field samples suggest that the changing leaf wax hydrogen isotopic fractionation in different terrestrial vascular plants may be related to different strategies in allocating photosynthetic substrates for metabolic and biosynthetic functions, and potential leaf water isotopic differences. PMID:25402476

  11. Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

    USGS Publications Warehouse

    Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

    2014-01-01

    RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

  12. Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.; Pizzarello, S.; Cronin, J. R.; Yuen, G. U.

    1991-01-01

    A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

  13. Hydrogen adsorption in metal-organic frameworks: the role of nuclear quantum effects.

    PubMed

    Wahiduzzaman, Mohammad; Walther, Christian F J; Heine, Thomas

    2014-08-14

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H2 in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H2 quantum fluid with increasing pressure and lowering temperature.

  14. Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

    NASA Astrophysics Data System (ADS)

    Wahiduzzaman, Mohammad; Walther, Christian F. J.; Heine, Thomas

    2014-08-01

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H2 in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H2 quantum fluid with increasing pressure and lowering temperature.

  15. Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

    SciTech Connect

    Wahiduzzaman, Mohammad; Walther, Christian F. J.; Heine, Thomas

    2014-08-14

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H{sub 2}-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H{sub 2} in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H{sub 2} quantum fluid with increasing pressure and lowering temperature.

  16. Molecular and dissociative adsorption of water and hydrogen sulfide at perfect and defective Cu(110) surfaces.

    PubMed

    Lousada, Cláudio M; Johansson, Adam Johannes; Korzhavyi, Pavel A

    2017-03-15

    We performed a density functional theory (DFT) investigation of the molecular and dissociative adsorption of H2O and H2S at perfect and defective Cu(110) surfaces described using supercells with c(6 × 6) periodicity. The defective surface consists of a terrace surrounded by pits. We found considerable differences in adsorption modes and energies for H2O and H2S. At the defective Cu(110) surface, monomers of H2O and H2S preferentially adsorb at the terrace site and molecular adsorption of H2O is significantly more favorable than that of H2S. For dissociative adsorption however, the sulfur species are considerably more stable than the oxygen species. For monolayer (ML) coverages, there are small differences in the molecular adsorption energies for H2O and H2S. However, for the formation of 1 ML of HO and 1 ML of HS from 1 ML of H2O and 1 ML of H2S, respectively, with the release of H2(g), the differences are very large. The formation of 1 ML HO at the perfect Cu(110) surface is endoergic, while at the defective Cu(110) surface it is exoergic by -0.6 eV. For high coverages, H2S forms stacked half-monolayers that interact with each other via a complex hydrogen bond network with a strength per H2S molecule of -0.140 eV per H2S and -0.120 eV per H2S for H2S located in the underlayer and overlayer, respectively. The large distances between hydrogen bonded H2S molecules explain the preference for the formation of the two stacked half-monolayers of H2S instead of a single monolayer as it happens with H2O. Additionally, the formation of 1 ML of HS does not occur because of the spontaneous splitting of some H-S bonds resulting in surface bound HS and S and H2S molecules. Extensive surface reconstruction and relaxation accompanies adsorption of the sulfur adsorbates. Such reconstructions with outwards pull of Cu atoms can be at the origin of the weak adhesion of sulfide films that explains the release of CuS particles from copper sulfide films at copper surfaces. Overall, the

  17. Effects of hydrogen isotope in coupling between confinement, wall material and SoL turbulence

    NASA Astrophysics Data System (ADS)

    Itoh, K.; Itoh, S.-I.; Sasaki, M.; Kosuga, Y.

    2017-05-01

    The hydrogen isotope effect on confinement is discussed by investigating the coupling between confinement, wall material and scrape-off-layer (SoL) turbulence. An emphasis is placed upon the dependence of the neutral density on the hydrogen mass number. The momentum loss via CX process in the barrier is studied, and its influence on the radial electric field in the barrier (so as to modify the suppression of transport) is discussed. The penetration of slow neutrals and the reflection of fast neutrals on the wall are considered. Combining these processes, the influence of hydrogen mass number on the atomic, molecular, material and plasma interactions is investigated. The penetration of strong fluctuations in the SoL plasma into the confined plasma via the fuelling of neutral particles (i.e. fuelling fuels turbulence) is also discussed. The hydrogen isotope effect on this source of edge turbulence, which can affect the core-confinement, is discussed.

  18. Selected bibliography on heavy water, tritiated water and hydrogen isotopes (1981-1992)

    NASA Astrophysics Data System (ADS)

    Gopalakrishnan, V. T.; Sutawane, U. B.; Rathi, B. N.

    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.

  19. Molecular adsorption of hydrogen peroxide on N- and Fe-doped titania nanoclusters

    NASA Astrophysics Data System (ADS)

    Mohajeri, Afshan; Dashti, Nasimeh Lari

    2017-06-01

    Titanium dioxide (titania) nanoparticles have been extensively investigated for photocatalytic applications such as the decomposition and adsorption of pollutant and undesirable compound in air and waste water. In this context, the present article reports the molecular adsorption of hydrogen peroxide on the surface of doped titania clusters. Density functional theory calculations were performed to investigate the structures and electronic properties of two nanoscale (TiO2)n clusters (n = 5,6) modified by nitrogen and iron dopants. The relative stability of all possible N-doped and Fe-doped isomers has been compared with each other and with the parent cluster. It was found that the Fe-doped clusters are in general more stable than the N-doped counterparts. Moreover, after N/Fe doping an enhanced in the magnetization of the clusters is observed. In the second part, we have investigated different modes of H2O2 adsorption on the lowest-energy isomers of doped clusters. In almost all the cases, the adsorptions on the doped clusters are found to be less exothermic than on the corresponding undoped parent cluster. Our results highlight the essential role of charge transfer into the interaction between H2O2 and doped (TiO2)n clusters, especially for Fe-doped clusters.

  20. Rapid adsorption removal of hydrogen sulfide by surface-modified activated carbon

    NASA Astrophysics Data System (ADS)

    Inoue, Akane; Matsumoto, Akihiko

    2017-07-01

    A coconut-shell-based activated carbon (AC) was oxidized by hydrogen preoxide solution to introduce oxygen-containing groups on the surface of AC (AC-HP). The concentration of the oxygen-containing groups was determined by the Boehm's method. The AC with highly dispersed zinc(II) oxide (AC-ZnO) or iron(II)iron(III) oxide (AC-Fe3O4) were also prepared by impregnation method. X-ray diffraction and TEM observation showed the formation of finely dispersed metal oxides on AC-ZnO and AC-Fe3O4. Adsorption features of H2S on these AC samples were characterized by flow adsorption technique. Remarkable difference in the adsorption capacity wasn't observed in AC and AC-HP. On the other hand, the H2S adsorption activity was significantly increased in AC-ZnO and AC-Fe3O4. The breakthrough curves of H2S on these AC samples indicate that AC-ZnO is the most promising candidate for the adsorbent of H2S.

  1. Isotope effects in dense solid hydrogen - Phase transition in deuterium at 190 + or - 20 GPa

    NASA Technical Reports Server (NTRS)

    Hemley, R. J.; Mao, H. K.

    1989-01-01

    Raman measurements of solid normal deuterium compressed in a diamond-anvil cell indicate that the material undergoes a structural phase transformation at 190 + or - 20 GPa and 77 K. Spectroscopically, the transition appears analogous to that observed in hydrogen at 145 + or - 5 GPa. The large isotope effect on the transition pressure suggests there is a significant vibrational contribution to the relative stability of the solid phases of hydrogen at very high densities.

  2. Adsorption and hydrogenation of simple alkenes at Pt-group metal electrodes studied by DEMS: influence of the crystal orientation

    NASA Astrophysics Data System (ADS)

    Müller, Ulrich; Schmiemann, Udo; Dülberg, Andreas; Baltruschat, Helmut

    1995-07-01

    The adsorption of ethene and cyclohexene on mono-and polycrystalline Pt and on polycrystalline Pd electrodes was studied using differential electrochemical mass spectrometry (DEMS). Both molecules are partially hydrated to an oxygen containing species upon adsorption on Pt. In the case of ethene, this species dissociated to methane and adsorbed CO at negative potentials. Another part of the adsorbed ethene can be cathodically desorbed as ethane and butane. The ratio of the various species formed strongly depends on crystal orientation and adsorption potential. Contrary to heterogenous gas phase hydrogenation (and also contrary to some earlier reports on electrochemical hydrogenation), the rate of the Faradaic hydrogenation reaction is also strongly dependent on the crystallographic orientation, being faster on Pt(110) or roughened surfaces. During hydrogenation, H/D exchange occurs to an appreciable degree, suggesting the participation of adsorbed intermediates.

  3. Holocene precipitation seasonality captured by a dual hydrogen and oxygen isotope approach at Steel Lake, Minnesota

    NASA Astrophysics Data System (ADS)

    Henderson, Anna K.; Nelson, David M.; Hu, Feng Sheng; Huang, Yongsong; Shuman, Bryan N.; Williams, John W.

    2010-12-01

    Middle-Holocene (8 to 4 ka BP) warmth and aridity are well recorded in sediment archives from midcontinental North America. However, neither the climatic driver nor the seasonal character of precipitation during this period is well understood because of the limitations of available proxy indicators. For example, an important challenge is to distinguish among the interacting effects of evaporation, temperature, or precipitation seasonality in existing δ 18O records from the region. Here we combine hydrogen isotopes of palmitic acid and oxygen isotopes of carbonate to derive lake-water isotopic values during the Holocene at Steel Lake in north-central Minnesota. In combination, these data enable us to separate variations in evaporation from variations in the isotopic composition of input-waters to lake. Variations in evaporation are used as a proxy for aridity and lake-water input isotopic values are used as a proxy for the isotopic values of meteoric precipitation. Our results suggest that lake-water input isotopic values were more negative during the middle Holocene than at present. To test whether these more negative values are related to temperature or precipitation seasonality, we compare pollen-inferred temperatures and the expected isotopic value of precipitation resulting from these temperatures to the reconstructed precipitation isotopic values. Results suggest that middle Holocene warmth and aridity were associated with increased evaporation rates and decreased summer precipitation. These inferences are consistent with climate simulations that highlight the role of seasonal insolation and sea surface temperatures in driving variations in precipitation seasonality during the Holocene. Results also suggest that changes in Holocene precipitation seasonality may have influenced the expansion of the prairie-forest border in Minnesota as well as regional variations in grassland community composition. This study demonstrates the efficacy of the dual hydrogen and

  4. Simulation of hydrogen adsorption systems adopting the flow through cooling concept

    SciTech Connect

    Corgnale, Claudio; Hardy, Bruce; Chahine, Richard; Cossement, Daniel; Tamburello, David; Anton, Donald

    2014-10-13

    Hydrogen storage systems based on adsorbent materials have the potential of achieving the U.S. Department of Energy (DOE) targets, especially in terms of gravimetric capacity. This paper deals with analysis of adsorption storage systems adopting the flow through cooling concept. By this approach the feeding hydrogen provides the needed cold to maintain the tank at low temperatures. Two adsorption systems have been examined and modeled adopting the Dubinin-Astakhov model, to see their performance under selected operating conditions. A first case has been analyzed, modeling a storage tank filled with carbon based material (namely MaxSorb®) and comparing the numerical outcomes with the available experimental results for a 2.5 L tank. Under selected operating conditions (minimum inlet hydrogen temperature of approximately 100 K and maximum pressure on the order of 8.5 MPa) and adopting the flow through cooling concept the material shows a gravimetric capacity of about 5.7 %. A second case has been modeled, examining the same tank filled with metal organic framework material (MOF5®) under approximately the same conditions. The model shows that the latter material can achieve a (material) gravimetric capacity on the order of 11%, making the system potentially able to achieve the DOE 2017 target.

  5. Simulation of hydrogen adsorption systems adopting the flow through cooling concept

    DOE PAGES

    Corgnale, Claudio; Hardy, Bruce; Chahine, Richard; ...

    2014-10-13

    Hydrogen storage systems based on adsorbent materials have the potential of achieving the U.S. Department of Energy (DOE) targets, especially in terms of gravimetric capacity. This paper deals with analysis of adsorption storage systems adopting the flow through cooling concept. By this approach the feeding hydrogen provides the needed cold to maintain the tank at low temperatures. Two adsorption systems have been examined and modeled adopting the Dubinin-Astakhov model, to see their performance under selected operating conditions. A first case has been analyzed, modeling a storage tank filled with carbon based material (namely MaxSorb®) and comparing the numerical outcomes withmore » the available experimental results for a 2.5 L tank. Under selected operating conditions (minimum inlet hydrogen temperature of approximately 100 K and maximum pressure on the order of 8.5 MPa) and adopting the flow through cooling concept the material shows a gravimetric capacity of about 5.7 %. A second case has been modeled, examining the same tank filled with metal organic framework material (MOF5®) under approximately the same conditions. The model shows that the latter material can achieve a (material) gravimetric capacity on the order of 11%, making the system potentially able to achieve the DOE 2017 target.« less

  6. Mechanism of hydrogen adsorption on gold nanoparticles and charge transfer probed by anisotropic surface plasmon resonance.

    PubMed

    Watkins, William L; Borensztein, Yves

    2017-10-03

    The adsorption of hydrogen on Au nanoparticles (NPs) of size of the order of 10 nm has been investigated by use of localised surface plasmon resonances (LSPR) in the NPs. The samples, formed by Au NPs obtained by oblique angle deposition on glass substrates, display a strong optical dichroism due to two different plasmon resonances dependent on the polarisation of light. This ensured the use of Transmittance Anisotropy Spectroscopy, a sensitive derivative optical technique, which permitted one to measure shifts of the LSPR as small as 0.02 nm upon H adsorption, which are not accessible by conventional plasmonic methods. The measured signal is proportional to the area of the NPs, which shows that H atoms diffuse on their facets. A negative charge transfer from Au to H is clearly demonstrated.

  7. Isotopes and analogs of hydrogen--from fundamental investigations to practical applications.

    PubMed

    Macrae, Roderick M

    2013-01-01

    Hydrogen has a central role in the story of the universe itself and also in the story of our efforts to understand it. This paper retells the story of the part played by hydrogen and its stable isotope deuterium in the primordial synthesis of the elements, then goes on to describe how the spectrum of atomic hydrogen led to insights into the laws governing matter at the most fundamental level, from the quantum mechanics of Schrödinger and Heisenberg, through quantum electrodynamics, to the most recent work investigating the underlying structure of the proton itself. Atomic hydrogen is unique among the elements in that the concept of isotopy--atoms having the same nuclear charge but different masses--is stretched to its limit in the isotopes of hydrogen, ranging from the well-known isotopes deuterium and tritium to exotic species such as muonium, muonic helium, and positronium. These atoms, or atom-like objects, have much to tell us about fundamental aspects of the universe. In recent years the idea of utilizing hydrogen either as an energy source (through nuclear fusion) or as an energy storage medium (bound in hydrides or other materials) has attracted much attention as a possible avenue to a post-oil energy future. Some of the more interesting recent developments are described here. Dedicated to the memory of Brian C. Webster (1939-2008).

  8. Influence of drinking water and diet on the stable-hydrogen isotope ratios of animal tissues

    PubMed Central

    Hobson, Keith A.; Atwell, Lisa; Wassenaar, Leonard I.

    1999-01-01

    Despite considerable interest in using stable-hydrogen isotope ratio (δD) measurements in ecological research, it was previously unknown whether hydrogen derived from drinking water, in addition to that derived from diet, contributed to the nonexchangeable hydrogen in animal tissues. We raised four experimental groups of quail (Coturnix coturnix japonica) from hatch on two isotopically distinct diets (mean nonexchangeable δD: −146 and −60‰, Vienna Standard Mean Ocean Water Standard) and drinking waters (mean δD: −130 and +196‰, Vienna Standard Mean Ocean Water Standard). Here we show that both dietary and drinking water hydrogen are incorporated into nonexchangeable hydrogen in both metabolically active (i.e., muscle, liver, blood, fat) and inactive (i.e., feather, nail) tissues. Approximately 20% of hydrogen in metabolically active quail tissues and 26–32% of feathers and nail was derived from drinking water. Our findings suggest environmental interpretations of δD values from modern and fossil animal tissues may need to account for potentially large isotopic differences between drinking water and food and require a good understanding of the physiological ecology of study organisms. PMID:10393937

  9. Influence of drinking water and diet on the stable-hydrogen isotope ratios of animal tissues.

    PubMed

    Hobson, K A; Atwell, L; Wassenaar, L I

    1999-07-06

    Despite considerable interest in using stable-hydrogen isotope ratio (deltaD) measurements in ecological research, it was previously unknown whether hydrogen derived from drinking water, in addition to that derived from diet, contributed to the nonexchangeable hydrogen in animal tissues. We raised four experimental groups of quail (Coturnix coturnix japonica) from hatch on two isotopically distinct diets (mean nonexchangeable deltaD: -146 and -60 per thousand, Vienna Standard Mean Ocean Water Standard) and drinking waters (mean deltaD: -130 and +196 per thousand, Vienna Standard Mean Ocean Water Standard). Here we show that both dietary and drinking water hydrogen are incorporated into nonexchangeable hydrogen in both metabolically active (i.e., muscle, liver, blood, fat) and inactive (i.e., feather, nail) tissues. Approximately 20% of hydrogen in metabolically active quail tissues and 26-32% of feathers and nail was derived from drinking water. Our findings suggest environmental interpretations of deltaD values from modern and fossil animal tissues may need to account for potentially large isotopic differences between drinking water and food and require a good understanding of the physiological ecology of study organisms.

  10. Spin-polarized hydrogen and its isotopes: A rich class of quantum phases (Review Article)

    NASA Astrophysics Data System (ADS)

    Bešlić, I.; Vranješ Markić, L.; Boronat, J.

    2013-10-01

    We review the recent activity in the theoretical description of spin-polarized atomic hydrogen and its isotopes at very low temperatures. Spin-polarized hydrogen is the only system in nature that remains stable in the gas phase even in the zero temperature limit due to its small mass and weak interatomic interaction. Hydrogen and its heavier isotope tritium are bosons, the heavier mass of tritium producing a self-bound (liquid) system at zero temperature. The other isotope, deuterium, is a fermion with nuclear spin one making possible the study of three different quantum systems depending on the population of the three degenerate spin states. From the theoretical point of view, spin-polarized hydrogen is specially appealing because its interatomic potential is very accurately known making possible its precise quantum many-body study. The experimental study of atomic hydrogen has been very difficult due to its high recombination rate, but it finally led to its Bose-Einstein condensate state in 1998. Degeneracy has also been observed in thin films of hydrogen adsorbed on the 4He surface allowing for the possibility of observing the Berezinskii-Kosterlitz-Thouless superfluid transition.

  11. Final Report: Characterization of Hydrogen Adsorption in Carbon-Based Materials by NMR

    SciTech Connect

    Wu, Yue; Kleinhammes, Alfred

    2011-07-11

    In support of DOE/EERE's Fuel Cell Technologies Program Hydrogen Sorption Center of Excellence (HSCoE), UNC conducted Nuclear Magnetic Resonance (NMR) measurements that contributed spectroscopic information as well as quantitative analysis of adsorption processes. While NMR based Langmuir isotherms produce reliable H2 capacity measurements, the most astute contribution to the center is provided by information on dihydrogen adsorption on the scale of nanometers, including the molecular dynamics of hydrogen in micropores, and the diffusion of dihydrogen between macro and micro pores. A new method to assess the pore width using H2 as probe of the pore geometry was developed and is based on the variation of the observed chemical shift of adsorbed dihydrogen as function of H2 pressure. Adsorbents designed and synthesized by the Center were assessed for their H2 capacity, the binding energy of the adsorption site, their pore structure and their ability to release H2. Feedback to the materials groups was provided to improve the materials’ properties. To enable in situ NMR measurements as a function of H2 pressure and temperature, a unique, specialized NMR system was designed and built. Pressure can be varied between 10-4 and 107 Pa while the temperature can be controlled between 77K and room temperature. In addition to the 1H investigation of the H2 adsorption process, NMR was implemented to measure the atomic content of substituted elements, e.g. boron in boron substituted graphitic material as well as to determine the local environment and symmetry of these substituted nuclei. The primary findings by UNC are the following: • Boron substituted for carbon in graphitic material in the planar BC3 configuration enhances the binding energy for adsorbed hydrogen. • Arrested kinetics of H2 was observed below 130K in the same boron substituted carbon samples that combine enhanced binding energy with micropore structure. • Hydrogen storage material made from activated

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Adsorption of hydrogen sulfide by biochars derived from pyrolysis of different agricultural/forestry wastes.

    PubMed

    Shang, Guofeng; Li, Qiwu; Liu, Liang; Chen, Ping; Huang, Xiamei

    2016-01-01

    The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different biochars derived from agricultural/forestry wastes through pyrolysis at various temperatures (100 to 500 ºC) were investigated. In this study, the H₂S breakthrough capacity was measured using a laboratory-characterized using pH and Fourier transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H2S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface. Certain threshold ranges of the pyrolysis temperature (from 100 to 500 ºC) and pH of the surface are presented. It also concluded that the sorption capacity (for removing H₂S) of rice hull-derived biochar is the largest in three biochars (camphor-derived biochar, rice hull-derived biochar, and bamboo-derived biochar). These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S. This paper focuses on the adsorption of hydrogen sulfide (H₂S) by biochars derived from wastes. The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different boichars derived from agricultural/forestry wastes through pyrolysis at various temperatures were investigated. In this study, the H₂S breakthrough capacity was measured using laboratory characterization with pH and Fourier-transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface.

  14. Electronic and optical properties of BxNyCz monolayers with adsorption of hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Leite, L.; Azevedo, S.; de Lima Bernardo, B.

    2017-03-01

    We apply first-principles calculations, using density functional theory, to analyze the electronic and optical properties of monolayers of graphene with a nanodomain of 2D hexagonal boron nitrite (h-BN). It also investigated the effects of the adsorption of hydrogen atoms in different atoms at the edge of the h-BN nanodomain. We calculate the electronic band structure, the complex dielectric function and the optical conductivity. For such systems, the calculations demonstrate that the compounds exhibit a prominent excitement in the visible and near-infrared regions. In this form, the present study provides physical basis for potential applications of the considered materials in optoelectronic devices at the nanoscale.

  15. Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

    USGS Publications Warehouse

    Coleman, D.D.; Risatti, J.B.; Schoell, M.

    1981-01-01

    Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

  16. Hydrogen and carbon isotope fractionation during degradation of chloromethane by methylotrophic bacteria

    PubMed Central

    Nadalig, Thierry; Greule, Markus; Bringel, Françoise; Vuilleumier, Stéphane; Keppler, Frank

    2013-01-01

    Chloromethane (CH3Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (ε) of −29‰ and −27‰ for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in 13C of untransformed CH3Cl was also observed, and similar isotope enrichment factors (ε) of −41‰ and −38‰ were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane. PMID:24019296

  17. Multi-saline sample distillation apparatus for hydrogen isotope analyses : design and accuracy

    USGS Publications Warehouse

    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)

  18. Application of Hydrogen Isotope Geochemistry to Volcanology: Recent Perspective on Eruption Dynamics

    SciTech Connect

    Nakamura, M.; Kasai, Y.; Sato, N.; Yoshimura, S.

    2008-02-25

    Degassing of magma is central to understand the dynamics of volcanic eruption. Hydrogen isotopic composition of volcanic rocks reflects degassing processes. The natural obsidian samples in some eruptions typically show a gently and then rapidly decreasing {delta}D trends with decreasing water content; this led to the two-stage degassing model, with closed-system volatile exsolution (batch fractionation of hydrogen isotope) during the explosive phase followed by open-system degassing (Rayleigh fractionation) to produce the low {delta}D value of the dome and flow lavas. However, the relationship between pattern of degassing (and fractionation) and mode of eruption is controversial. Based on the CO{sub 2}/H{sub 2}O ratio of the obsidians, Rust et al. suggested that the analyzed samples with relatively constant {delta}D value and high water content were buffered (re-equilibrated) with vapor of relatively constant isotopic composition, assuming that silicic magma along conduit wall is fragmented and highly permeable. However, the timing and mechanism of the shift to open system degassing (Rayleigh fractionation) has not been clarified. To further constrain the eruption dynamics, experimental study on the hydrogen isotope fractionation during degassing would be helpful, although common noble metals used as sample capsules, including Au, are permeable to hydrogen at magmatic temperature, and even to water molecule in the prolonged run, probably due to the change of grain boundary properties such as thermal grooving.

  19. Assessing carbon and hydrogen isotopic fractionation of diesel fuel n-alkanes during progressive evaporation.

    PubMed

    Muhammad, Syahidah A; Hayman, Alan R; Van Hale, Robert; Frew, Russell D

    2015-01-01

    Compound-specific isotope analysis offers potential for fingerprinting of diesel fuels, however, possible confounding effects of isotopic fractionation due to evaporation need to be assessed. This study measured the fractionation of the stable carbon and hydrogen isotopes in n-alkane compounds in neat diesel fuel during evaporation. Isotope ratios were measured using a continuous flow gas chromatograph/isotope ratio mass spectrometer. Diesel samples were progressively evaporated at 24 ± 2°C for 21 days. Increasing depletion of deuterium in nC12-nC17 alkanes in the remaining liquid with increasing carbon chain length was observed. Negligible carbon isotope fractionation was observed. Preferential vaporization was measured for the shorter chain n-alkanes and the trend decreased with increasing chain length. The decrease in δ(2) H values indicates the preferential vaporization of the isotopically heavier species consistent with available quantitative data for hydrocarbons. These results are most important in the application of stable isotope technology to forensic analysis of diesel.

  20. Coupled Oxygen and Hydrogen Isotope Analysis of Water Along the Soil-Plant- Atmosphere Continuum

    NASA Astrophysics Data System (ADS)

    Huang, Z.; Webb, E. A.; Longstaffe, F. J.

    2008-12-01

    The oxygen and hydrogen isotope compositions of water within a plant vary with transpiration rates and the isotopic composition of soil water. Both of these parameters are affected by temperature and relative humidity. A controlled-temperature, growth-chamber experiment was conducted to determine the relationships among temperature, relative humidity, soil water evaporation and plant-water isotope composition in cattails and horsetails. Typha, a cattail species that grows in wetland conditions, and Equisetum, a horsetail species that prefers dry soils, were each grown in four chambers at 15, 20, 25 and 30 degrees Celsius. The oxygen and hydrogen isotope compositions of watering water, soil water, vapour in the growth chambers and plant water from the leaves and stems were analyzed throughout the eight-month long artificial growing season. Although the oxygen isotope composition of the watering water remained constant, the soil water, atmospheric vapour and plant water were progressively enriched in oxygen-18 and deuterium in each of the four chambers from low to high temperatures as a result of increasing evaporation. The oxygen isotope composition of plant water along the length of a single stem or leaf was increasingly enriched in the heavier isotopes towards the apex. There was no significant difference in the magnitude of this trend between species. These results indicate that the isotopic composition of plant water is primarily controlled by environmental conditions. The oxygen isotope composition of the water vapour in the growing chamber increased with temperature, consistent with equilibration between the vapour and the oxygen-18 enriched soil and plant water reservoirs. The magnitude and interaction of these variables, as measured for these modern samples of cattails and horsetails, should be useful in calibrating paleoclimate proxies based on fossilized plant materials (e.g., cellulose, phytoliths).

  1. Hydrogen isotope separation installation for the regeneration of tritium from gas mixtures in tritium facilities

    SciTech Connect

    Andrew, B.M.; Perevezentsev, A.N.; Selivanenko, I.L.

    1994-12-31

    The advantages and disadvantages of different methods for hydrogen isotope separation are considered in terms of their applicability for tritium regeneration in a tritium facility. Due to low inventory, simplicity of operation, flexibility, and safety the methods of separation using solid phases are preferable for tritium facility. The detail consideration of the separation processes with a solid phase reveals that highest efficiency of separation should be achieved in a counter-current separation column, which allow multiplying the thermodynamic isotopic effect. Because of difficulties of the organization of a solid phase motion in a separation column this method did not found practical application for separation of hydrogen isotopic mixtures. The main efforts of a few researches groups were devoted to improve the chromatographic separation process and equipment. The detail comparison of the separation in sectioned column with that in chromatographic as well as in cryodistillation columns show that counter-current separation in a sectioned column is more effective and has other advantages when middle throughput is required. Complete regeneration of an isotopic mixture with separation into three practically pure isotopes independently from isotopic composition of feed can be provided using two sectioned separation columns. Separation installation can operate continuously as well as periodically.

  2. Hydrogen isotopic profile in the characterization of sugars. Influence of the metabolic pathway.

    PubMed

    Zhang, Ben-Li; Billault, Isabelle; Li, Xiaobao; Mabon, Françoise; Remaud, Gérald; Martin, Maryvonne L

    2002-03-13

    The site-specific natural hydrogen isotope ratios of plant metabolites determined by 2H nuclear magnetic resonance (SNIF-NMR method) can provide powerful criteria for inferring mechanistic and environmental effects on biosynthetic pathways. This work examines the potential of isotopic profiles for the main constituents of carbohydrates, glucose and fructose, to distinguish different photosynthetic pathways. An appropriate analytical strategy, involving three suitable isotopic probes, has been elaborated with a view to measuring simultaneously, in conditions devoid of isotopic perturbations, all (or nearly all) of the carbon-bound hydrogen isotope ratios. It is shown that the type of photosynthetic metabolism, either C3 (sugar beet, orange, and grape), C4 (maize and sugar cane), or CAM (pineapple), and the physiological status of the precursor plant exert strong influences on the deuterium distribution in the sugar molecules. Consequently, this isotopic fingerprint may be a rich source of information for the comparison of mechanisms in metabolic pathways. In addition, it can provide complementary criteria to ethanol as a probe for the origin of sugars.

  3. Adsorption of hydrogen on neutral and charged fullerene: experiment and theory.

    PubMed

    Kaiser, A; Leidlmair, C; Bartl, P; Zöttl, S; Denifl, S; Mauracher, A; Probst, M; Scheier, P; Echt, O

    2013-02-21

    Helium droplets are doped with fullerenes (either C60 or C70) and hydrogen (H2 or D2) and investigated by high-resolution mass spectrometry. In addition to pure helium and hydrogen cluster ions, hydrogen-fullerene complexes are observed upon electron ionization. The composition of the main ion series is (H2)(n)HC(m)(+) where m = 60 or 70. Another series of even-numbered ions, (H2)(n)C(m)(+), is slightly weaker in stark contrast to pure hydrogen cluster ions for which the even-numbered series (H2)(n)(+) is barely detectable. The ion series (H2)(n)HC(m)(+) and (H2)(n)C(m)(+) exhibit abrupt drops in ion abundance at n = 32 for C60 and 37 for C70, indicating formation of an energetically favorable commensurate phase, with each face of the fullerene ion being covered by one adsorbate molecule. However, the first solvation layer is not complete until a total of 49 H2 are adsorbed on C60(+); the corresponding value for C70(+) is 51. Surprisingly, these values do not exhibit a hydrogen-deuterium isotope effect even though the isotope effect for H2/D2 adsorbates on graphite exceeds 6%. We also observe doubly charged fullerene-deuterium clusters; they, too, exhibit abrupt drops in ion abundance at n = 32 and 37 for C60 and C70, respectively. The findings imply that the charge is localized on the fullerene, stabilizing the system against charge separation. Density functional calculations for C60-hydrogen complexes with up to five hydrogen atoms provide insight into the experimental findings and the structure of the ions. The binding energy of physisorbed H2 is 57 meV for H2C60(+) and (H2)2C60(+), and slightly above 70 meV for H2HC60(+) and (H2)2HC60(+). The lone hydrogen in the odd-numbered complexes is covalently bound atop a carbon atom but a large barrier of 1.69 eV impedes chemisorption of the H2 molecules. Calculations for neutral and doubly charged complexes are presented as well.

  4. Adsorption of hydrogen on neutral and charged fullerene: Experiment and theory

    SciTech Connect

    Kaiser, A.; Leidlmair, C.; Bartl, P.; Zoettl, S.; Denifl, S.; Mauracher, A.; Probst, M.; Scheier, P.; Echt, O.

    2013-02-21

    Helium droplets are doped with fullerenes (either C{sub 60} or C{sub 70}) and hydrogen (H{sub 2} or D{sub 2}) and investigated by high-resolution mass spectrometry. In addition to pure helium and hydrogen cluster ions, hydrogen-fullerene complexes are observed upon electron ionization. The composition of the main ion series is (H{sub 2}){sub n}HC{sub m}{sup +} where m= 60 or 70. Another series of even-numbered ions, (H{sub 2}){sub n}C{sub m}{sup +}, is slightly weaker in stark contrast to pure hydrogen cluster ions for which the even-numbered series (H{sub 2}){sub n}{sup +} is barely detectable. The ion series (H{sub 2}){sub n}HC{sub m}{sup +} and (H{sub 2}){sub n}C{sub m}{sup +} exhibit abrupt drops in ion abundance at n= 32 for C{sub 60} and 37 for C{sub 70}, indicating formation of an energetically favorable commensurate phase, with each face of the fullerene ion being covered by one adsorbate molecule. However, the first solvation layer is not complete until a total of 49 H{sub 2} are adsorbed on C{sub 60}{sup +}; the corresponding value for C{sub 70}{sup +} is 51. Surprisingly, these values do not exhibit a hydrogen-deuterium isotope effect even though the isotope effect for H{sub 2}/D{sub 2} adsorbates on graphite exceeds 6%. We also observe doubly charged fullerene-deuterium clusters; they, too, exhibit abrupt drops in ion abundance at n= 32 and 37 for C{sub 60} and C{sub 70}, respectively. The findings imply that the charge is localized on the fullerene, stabilizing the system against charge separation. Density functional calculations for C{sub 60}-hydrogen complexes with up to five hydrogen atoms provide insight into the experimental findings and the structure of the ions. The binding energy of physisorbed H{sub 2} is 57 meV for H{sub 2}C{sub 60}{sup +} and (H{sub 2}){sub 2}C{sub 60}{sup +}, and slightly above 70 meV for H{sub 2}HC{sub 60}{sup +} and (H{sub 2}){sub 2}HC{sub 60}{sup +}. The lone hydrogen in the odd-numbered complexes is covalently bound

  5. Adsorption Behavior of Metasilicate on N-Methyl d-Glucamine Functional Groups and Associated Silicon Isotope Fractionation.

    PubMed

    Wang, Wei; Wei, Hai-Zhen; Jiang, Shao-Yong; Eastoe, Christopher J; Guo, Qi; Lin, Yi-Bo

    2016-09-06

    Significant isotope fractionation of silicon provides a powerful geochemical tracer for biological and physicochemical processes in terrestrial and marine environments. The exact mechanism involved in silicon uptake as part of the biological process is not well known. The silicon uptake in biological processes is investigated using silicate adsorption onto the N-methylglucamine functional group (sugarlike structure, abbreviated as L) of Amberlite IRA-743 resin as an analogue of the formation of silicate-sugar complexes in plants. This study provides new evidence that certain sugars can react readily with basic silicic acid to form sugar-silicate chelating complexes, and the equilibrium adsorption behavior of silicate can be well described by the Langmuir isotherm with a Gibbs free energy (ΔG) of -11.94 ± 0.21 kJ·mol(-1) at 293 K. The adsorption kinetics corresponds well to a first-order kinetic model in which the adsorption rate constant ka of 1.25 × 10(-4) s(-1) and the desorption rate constant kd of 4.00 × 10(-6) s(-1) are obtained at 293 K. Both ka and kd increase with increasing temperature. The bonding configurations of silicate-sugar complexes imply the principal coordination complex of hexacoordinated silicon (silicon/L = 1:3) in the liquid phase and the dominant tetracoordinated silicon in the solid phase. Similar to those of many natural processes, the biological uptake via the sugar-silicate chelating complexes favors the preferential enrichment of light Si isotopes into solids, and the Rayleigh model controls the dynamic isotope fractionation with an estimated silicon isotope fractionation factor (i.e., αsolid-solution = [Formula: see text]) of 0.9971. This study advanced the fundamental understanding of the dynamic isotope fractionation of silicon during silicon cycling from the lithosphere to the biosphere and hydrosphere in surficial processes.

  6. Use of H/D isotope effects to gather information about hydrogen bonding and hydrogen exchange rates.

    PubMed

    Takeda, Mitsuhiro; Miyanoiri, Yohei; Terauchi, Tsutomu; Yang, Chun-Jiun; Kainosho, Masatsune

    2014-04-01

    Polar side-chains in proteins play important roles in forming and maintaining three-dimensional structures, and thus participate in various biological functions. Until recently, most protein NMR studies have focused on the non-exchangeable protons of amino acid residues. The exchangeable protons attached to polar groups, such as hydroxyl (OH), sulfhydryl (SH), and amino (NH2) groups, have mostly been ignored, because in many cases these hydrogen atoms exchange too quickly with water protons, making NMR observations impractical. However, in certain environments, such as deep within the hydrophobic interior of a protein, or in a strong hydrogen bond to other polar groups or interacting ligands, the protons attached to polar groups may exhibit slow hydrogen exchange rates and thus become NMR accessible. To explore the structural and biological implications of the interactions involving polar side-chains, we have developed versatile NMR methods to detect such cases by observing the line shapes of (13)C NMR signals near the polar groups, which are affected by deuterium-proton isotope shifts in a mixture of H2O and D2O. These methods allow the detection of polar side-chains with slow hydrogen-deuterium exchange rates, and therefore provide opportunities to retrieve information about the polar side-chains, which might otherwise be overlooked by conventional NMR experiments. Future prospects of applications using deuterium-proton isotope shifts to retrieve missing structural and dynamic information of proteins are discussed.

  7. Hydrogen adsorption and diffusion, and subcritical-crack growth in high strength steels and nickel base alloys

    NASA Technical Reports Server (NTRS)

    Wei, R. P.; Klier, K.; Simmons, G. W.; Chornet, E.

    1973-01-01

    Embrittlement, or the enhancement of crack growth by gaseous hydrogen in high strength alloys, is of primary interest in selecting alloys for various components in the space shuttle. Embrittlement is known to occur at hydrogen gas pressures ranging from fractions to several hundred atmospheres, and is most severe in the case of martensitic high strength steels. Kinetic information on subcritical crack growth in gaseous hydrogen is sparse at this time. Corroborative information on hydrogen adsorption and diffusion is inadequate to permit a clear determination of the rate controlling process and possible mechanism in hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Therefore, coordinated studies of the kinetics of crack growth, and adsorption and diffusion of hydrogen, using identical materials, have been initiated. Comparable conditions of temperature and pressure will be used in the chemical and mechanical experiments. Inconel 718 alloy and 18Ni(200) maraging steel have been selected for these studies. Results from these studies are expected to provide not only a better understanding of the gaseous hydrogen embrittlement phenomenon itself, but also fundamental information on hydrogen adsorption and diffusion, and crack growth information that can be used directly for design.

  8. The effect of amorphous silicon surface hydrogenation on morphology, wettability and its implication on the adsorption of proteins

    NASA Astrophysics Data System (ADS)

    Filali, Larbi; Brahmi, Yamina; Sib, Jamal Dine; Bouhekka, Ahmed; Benlakehal, Djamel; Bouizem, Yahya; Kebab, Aissa; Chahed, Larbi

    2016-10-01

    We study the effect of amorphous silicon (a-Si) surface hydrogenation on Bovine Serum Albumin (BSA) adsorption. A set of (a-Si) films was prepared by radio frequency magnetron sputtering (RFMS) and after deposition; they were treated in molecular hydrogen ambient at different pressures (1-3 Pa). Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy and spectroscopic ellipsometry (SE) were used to study the hydrogenation effect and BSA adsorption. Atomic force microscopy (AFM) was used to evaluate morphological changes caused by hydrogenation. The wettability of the films was measured using contact angle measurement, and in the case of the hydrogenated surfaces, it was found to be driven by surface roughness. FTIR-ATR spectroscopy and SE measurements show that proteins had the strongest affinity toward the surfaces with the highest hydrogen content and their secondary structure was affected by a significant decrease of the α-helix component (-27%) compared with the proteins adsorbed on the un-treated surface, which had a predominantly α-helix (45%) structure. The adsorbed protein layer was found to be densely packed with a large thickness (30.9 nm) on the hydrogen-rich surfaces. The most important result is that the surface hydrogen content was the dominant factor, compared to wettability and morphology, for protein adsorption.

  9. Using Stable Isotopes to Trace Microbial Hydrogen Production Pathways

    NASA Astrophysics Data System (ADS)

    Moran, J.; Hill, E.; Bartholomew, R.; Yang, H.; Shi, L.; Ostrom, N. E.; Gandhi, H.; Hegg, E.; Kreuzer, H.

    2010-12-01

    Biological H2 production by hydrogenase enzymes (H2ases) plays an important role in anaerobic microbial metabolism and community structure. Despite considerable progress in elucidating H2 metabolism, the regulation of and flux through key H2 production pathways remain largely undefined. Our goal is to improve understanding of biological H2 production by using H isotope ratios to dissect proton fluxes through different H2ase enzymes and from different substrates. We hypothesized that the isotope ratio of H2 produced by various hydrogenases (H2ase) would differ, and that the H isotope ratios would allow us to define the contribution of different enzymes when more than one is present in vivo. We chose Shewanella oneidensis (S.o.) MR-1, a facultative anaerobe capable of transferring electrons to a variety of terminal acceptors, including protons, as a model system for in vivo studies. S. o. encodes one [FeFe]- and one [NiFe]-H2ase. We purified three [FeFe]-H2ases (S.o., Clostridium pasteurianum, and Chlamydomonas reinhardtii) and two [NiFe]-H2ases (S. o. and Desulfovibrio fructosovorans) to test the isotope fractionation associated with activity by each enzyme in vitro. For in vivo analysis we used wild-type S.o. as well as electron transfer-deficient and H2ase-deficient strains. We employed batch cultures using lactate as an electron donor and O2 as an initial electron acceptor (with H2 production after O2 consumption). The five H2ases we tested all had a unique isotope fractionation. Measurements of H2 produced in vivo showed distinct periods of H2 production having isotope signatures consistent with in vitro results. Isotope data as well as studies of H2 production by mutants in the genes encoding either the [NiFe]-H2ase or the [FeFe]-H2ase, respectively, show that the [NiFe]- and [FeFe]- H2ases became active at different times. The [NiFe]-H2ase both produces and consumes H2 before the [FeFe]-H2ase becomes active. RNA analysis is consistent with up regulation of

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Hydrogen isotopic composition of the water in CR chondrites

    NASA Astrophysics Data System (ADS)

    Bonal, L.; Alexander, C. M. O.'D.; Huss, G. R.; Nagashima, K.; Quirico, E.; Beck, P.

    2013-04-01

    The thermal and aqueous alteration experienced by QUE 99177, MET 00426, EET 92042, GRA 95229, Renazzo and Al Rais CR chondrites was assessed through multi-technique characterization of their the carbonaceous matter and hydrated mineral phases. Each of the chondrites escaped long duration thermal metamorphism as reflected by the low structural order of the polyaromatic carbonaceous matter assessed by Raman spectroscopy. The infrared spectra of the matrix grains clearly reveal the presence of hydrated minerals in each of the CR chondrites. In particular, the extent of aqueous alteration experienced by QUE 99177 and MET 00426 may have been previously underestimated. The H isotopic compositions of the altering fluids were measured in situ in fine-grained phyllosilicates and individual coarse-grained hydrated silicates. In the analyzed CR chondrites, the main observations are that (i) the water is systematically enriched in D, and the enrichments (δDwater up to 1600‰) can be even higher than the highest D-enrichments reported for cometary water; (ii) the isotopic composition of the water is highly variable at the micrometer scale; (iii) there is no clear trend observed in the isotopic composition of the water (maximum D-enrichment, range of variation) along the aqueous alteration sequence. The D-enrichments and spatial variability are easier to explain as secondary signatures acquired through parent body processes, rather than as being due to the accretion of at least two ices with distinct isotopic compositions and sources that did not fully mix when they melted at the start of the aqueous alteration process.

  12. Preparation of Graphene with Graphane Areas of Controlled Hydrogen Isotope Composition on Opposite Sides.

    PubMed

    Balgar, Thorsten; Kim, Hyunil; Hasselbrink, Eckart

    2013-06-20

    Monolayer graphene was prepared on an Ir(111) substrate where it exhibits a 25 × 25 Å(2) moiré pattern. Molecular hydrogen was dosed first, allowing it to dissociate on open areas of the Ir substrate. The generated H atoms formed an intercalated reservoir that can bind to the graphene subsequently. Next, atomic hydrogen was dosed, which binds to the graphene sheet and also initiates the transfer of H from the Ir substrate to the graphene sheet. The opposite sides of the sheet can be hydrogenated with isotope selectivity, as a sequence of difference isotopes, H or D, can be chosen at will in the preparation procedure. Sum-frequency generation spectra prove that as consequence of the dosing sequence, C-H bonds are predominantly pointing toward the Ir substrate side when H2 is dosed first and alternatively toward the vacuum side when D2 is dosed first.

  13. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

    PubMed

    O'Grady, Shannon P; Valenzuela, Luciano O; Remien, Christopher H; Enright, Lindsey E; Jorgensen, Matthew J; Kaplan, Jay R; Wagner, Janice D; Cerling, Thure E; Ehleringer, James R

    2012-07-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems.

  14. Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

    PubMed Central

    O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

    2012-01-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

  15. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

    DOE PAGES

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

    2013-06-03

    Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorptionmore » of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.« less

  16. Adsorption and recombination of hydrogen atoms on a model graphite surface. [in interstellar space

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.; Chang, S.

    1985-01-01

    The adsorption and recombination of atomic hydrogen on a model graphite grain have been examined in a series of calculations in which a modified, iterative, extended Hueckel program was used. The hydrogen atom is found to be chemisorbed at a site with a zero-point binding energy of 0.7 eV and at an equilibrium distance of 2.25 A above the site. Despite a barrier of about 0.4 eV between adjacent sites, calculations suggest that at temperatures as low as 10 K, an H atom will tunnel through to adjacent sites in less than one nanosecond. However, a potential barrier to the recombination of two hydrogen atoms has been found which displays high sensitivity to the mutual arrangement of the two hydrogen atoms with respect to the graphite surface. Results show that at very low temperatures, recombinations can occur only by tunneling. Consistent with experiment, the region in which H2 begins to form exhibits a repulsive potential with respect to possible chemisorption of the incipient H2 entity.

  17. Enhanced hydrogen adsorption on Li-coated B12C6N6

    NASA Astrophysics Data System (ADS)

    Jin, Xueling; Qi, Pengtang; Yang, Huihui; Zhang, Yan; Li, Jinyun; Chen, Hongshan

    2016-10-01

    The hydrogen storage property of Li-coated B12C6N6 is investigated by density functional theory calculations. B12C6N6 is an electron deficient fullerene. Li atoms can be strongly bound to this cage by donating their valance electrons to the virtual 2p orbitals of carbon in the cluster. The binding energy (-2.90 eV) is much larger than the cohesive energy (1.63 eV) of bulk Li, and it prevents the Li atoms from aggregation. The coated Li atoms have large positive charges and the adsorbed hydrogen molecules can be moderately polarized by the Li+ ions. The computation shows that each Li atom coated on B12C6N6 can hold 2-3 H2 molecules with adsorption energies in the range of 0.21-0.24 eV/H2. The B12C6N6Li8 can adsorb 16 H2 and achieve a gravimetric hydrogen density of 8.63 wt. %. The present results indicate that alkali-metal atoms coated on electron deficient fullerenes can serve as hydrogen storage materials that can operate at ambient temperatures with high recycling storage capacity.

  18. Enhanced hydrogen adsorption on Li-coated B12C6N6.

    PubMed

    Jin, Xueling; Qi, Pengtang; Yang, Huihui; Zhang, Yan; Li, Jinyun; Chen, Hongshan

    2016-10-28

    The hydrogen storage property of Li-coated B12C6N6 is investigated by density functional theory calculations. B12C6N6 is an electron deficient fullerene. Li atoms can be strongly bound to this cage by donating their valance electrons to the virtual 2p orbitals of carbon in the cluster. The binding energy (-2.90 eV) is much larger than the cohesive energy (1.63 eV) of bulk Li, and it prevents the Li atoms from aggregation. The coated Li atoms have large positive charges and the adsorbed hydrogen molecules can be moderately polarized by the Li(+) ions. The computation shows that each Li atom coated on B12C6N6 can hold 2-3 H2 molecules with adsorption energies in the range of 0.21-0.24 eV/H2. The B12C6N6Li8 can adsorb 16 H2 and achieve a gravimetric hydrogen density of 8.63 wt. %. The present results indicate that alkali-metal atoms coated on electron deficient fullerenes can serve as hydrogen storage materials that can operate at ambient temperatures with high recycling storage capacity.

  19. Structure and Hydrogen Adsorption Properties of SBA-15 Doped with Pd Nanoparticles.

    PubMed

    Lee, Sang-Hwa; Park, Taehee; Yi, Whikun; Kim, Jaeyong

    2015-11-01

    Hydrogen adsorption properties of Pd-doped Santa Barbara amorphous No. 15 (Pd-SBA-15) were investigated and the results were compared with pure SBA-15 ones in terms of change of its structure and Pd concentration. Pd-SBA-15 samples were prepared by a hydrothermal reaction, using mixture of PEO20PPO70PEO20 (P123) and tetraethyl orthosilicate (TEOS). For the doping of Pd on SBA-15, PdC2 solution was added into the mixture of P123 and TEOS, and the solution was annealed at 80 degrees C for 2 hours under 800 Torr of hydrogen atmosphere. According to the X-ray diffraction and transmission electron microscope data, Pd-doped SBA-15 samples form a hexagonal array of mesoporous structure with 20-30 nm size of Pd particles. Values of specific surface area decreased from 630 to 414 m2/g as increasing the Pd doping level due to the increasing of the volume density. In fact, the volume density increased from 0.103 to 0.276 g/cc as increasing the mass ratio of PdCl2 to TEOS from 0 to 0.5. For the Pd-doped SBA-15, the amount of adsorbed hydrogen significantly increased from 0.49 to 0.99 wt% as increasing the Pd doping level from 0 to 0.5 demonstrating that Pd doping is an effect method for SBA-1 5 as a potential use of hydrogen storage application.

  20. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces.

    PubMed

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; Bartynski, Robert A

    2013-08-21

    We report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.

  1. Hydrogen adsorption and storage on Palladium - functionalized graphene with NH-dopant: A first principles calculation

    NASA Astrophysics Data System (ADS)

    Faye, Omar; Szpunar, Jerzy A.; Szpunar, Barbara; Beye, Aboubaker Chedikh

    2017-01-01

    We conducted a detailed theoretical investigation of the structural and electronic properties of single and double sided Pd-functionalized graphene and NH-doped Pd-functionalized graphene, which are shown to be efficient materials for hydrogen storage. Nitrene radical dopant was an effective addition required for enhancing the Pd binding on the graphene sheet as well as the storage of hydrogen. We found that up to eight H2 molecules could be adsorbed by double-sided Pd-functionalized graphene at 0 K with an average binding energy in the range 1.315-0.567 eVA gravimetric hydrogen density of 3.622 wt% was reached in the Pd-functionalized graphene on both sides. The binding mechanism of H2 molecules came not only the polarization mechanism between Pd and H atoms but also from the binding of the Pd atoms on the graphene sheet and the orbital hybridization. The most crucial part of our work is measuring the effect of nitrene radical on the H2 adsorption on Pd-functionalized graphene. Our calculations predicted that the addition of NH radicals on Pd-functionalized graphene enhance the binding of H2 molecules, which helps also to avoid the desorption of Pd(H2)n (n = 1-5) complexes from graphene sheet. Our results also predict Pd-functionalized NH-doped graphene is a potential hydrogen storage medium for on-board applications.

  2. Changes in hydrogen isotope ratios in sequential plumage stages: an implication for the creation of isotope-base maps for tracking migratory birds.

    PubMed

    Duxbury, J M; Holroyd, G L; Muehlenbachs, K

    2003-09-01

    Accurate reference maps are important in the use of stable-isotopes to track the movements of migratory birds. Reference maps created by the analysis of samples collected from young at the nest site are more accurate than simply referring to naturally occurring patterns of hydrogen isotope ratios created by precipitation cycles. Ratios of hydrogen isotopes in the nutrients incorporated early in the development of young birds can be derived from endogenous, maternal sources. Base-maps should be created with the analysis of tissue samples from hatchlings after local the isotopic signature of exogenous nutrients is dominant. Migratory species such as Peregrine Falcons are known to use endogenous sources in the creation of their eggs, therefore knowledge of what plumage stage best represents the local hydrogen ratios would assist in the planning of nest visits. We conducted diet manipulation experiments involving Japanese Quail and Peregrine Falcons to determine the plumage stage when hydrogen isotope ratios were indicative of a switch in their food source. The natal down of both the quail and falcons reflected the diet of breeding adult females. The hydrogen isotope ratios of a new food source were dominant in the juvenile down of the young falcons, although a further shift was detected in the final juvenile plumage. The juvenile plumage is grown during weeks 3-4 after hatch on Peregrine Falcons. Nest visits for the purpose of collecting feathers for isotope-base-map creation should be made around 4 weeks after the presumed hatch of the young falcons.

  3. Observations of hydrogen and helium isotopes in solar cosmic rays. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Hurford, G. J.

    1974-01-01

    The isotopic composition of hydrogen and helium in solar cosmic rays provides a means of studying solar flare particle acceleration mechanisms since the enhanced relative abundance of rare isotopes, such as H-2, H-3, and He-3, is due to their production by inelastic nuclear collisions in the solar atmosphere during the flare. Electron isotope spectrometer on an IMP spacecraft was used to measure this isotopic composition. The response of the dE/dx-E particle telescope is discussed, and alpha particle channeling in thin detectors is identified as an important background source affecting measurement of low values of (He-3/He-4). The flare-averaged results obtained for the period October, 1972 November, 1973 are given.

  4. Hydrogen adsorption on Be, Mg, Ca and Sr doped graphenes: The role of the dopant in the IIA main group

    NASA Astrophysics Data System (ADS)

    Luo, Huijuan; Li, Hejun; Fu, Qiangang

    2017-02-01

    Hydrogen (H2) adsorption on the IIA elements doped double-vacancy graphenes (BeG, MgG, CaG and SrG) was studied by using dispersion-corrected density functional theory calculations. Through investigation of different numbers of hydrogen dockings from two directions, it is found that 1H2/BeG, 1H2/MgG, 8H2/CaG and 8H2/SrG are the most stable adsorption configurations for Be, Mg, Ca and Sr doped graphenes, respectively. Atomic radius, electronegativity and ionization potential of the IIA dopant contribute to the dominating adsorption mechanism under specific H2 concentration. The study would facilitate exploration of high performance graphene-related supports for hydrogen storage.

  5. Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

    NASA Astrophysics Data System (ADS)

    Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

    2016-12-01

    Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen

  6. Genesis and evolution of water in a two-mica pluton: A hydrogen isotope study

    USGS Publications Warehouse

    Brigham, R.H.; O'Neil, J.R.

    1985-01-01

    Measurements were made of the hydrogen isotope composition of 74 samples of muscovite, biotite, vein quartz and whole rocks from the Papoose Flat pluton, eastern California, U.S.A., and adjacent metamorphic and sedimentary rocks in order to elucidate the genesis and evolution of water and hydrous minerals in a two-mica granodiorite. Electron microprobe analyses were made of all micas so that the Suzuoki-Epstein equation could be used in evaluating the data. Based on experimental, theoretical and textural evidence of mica paragenesis, a model of hydrogen isotope fractionation between an aqueous vapor and a magma during crystallization has been constructed. This model accounts for the observed hydrogen isotope relations and implies that primary hydrogen isotope compositions have been preserved in a large portion of the pluton. The ?? D-values of biotites vary widely over the range -103 to -66% with most values lying between -90 and -70??? Muscovites, on the other hand, are isotopically more uniform and have ?? D-values of -61 to -41??? with most values lying between -50 and -46??? These data are consistent with the interpretation that biotite formed over a long period of crystallization whereas muscovite formed in a narrow interval, presumably during the final stages of crystallization when alumina and water contents were at their highest. Only 8 of the 21 muscovite-biotite pairs analyzed are in hydrogen isotope equilibrium as calculated from the Suzuoki-Epstein equation. Biotites in the western half of the pluton have relatively low ?? D-values of around -85???, whereas those in the eastern half have higher values of up to -66??? This pattern is a consequence of a loss of permeability associated with the syn-intrusive deformation of the western margin of the pluton. This loss of permeability enhanced the preservation of primary hydrogen isotope relations there by diverting water evolved from the magma out through the eastern half of the pluton where some deuteric

  7. Hydrogen isotopes from source water to leaf lipid in a continental-scale sample network

    NASA Astrophysics Data System (ADS)

    Nelson, Daniel; Kahmen, Ansgar

    2015-04-01

    Sedimentary plant waxes are useful paleoclimate proxies because they are preserved in depositional settings on geologic timescales and the isotopic composition of the hydrogen in these molecules reflects that of the source water available during biosynthesis. This application is based largely on empirical calibrations that have demonstrated continental-scale correlations between source water and lipid hydrogen isotope values. However, the importance of variable net isotopic fractionation between source water and lipid for different species and environmental conditions is increasingly recognized. Isotopic enrichment of leaf water during transpiration is key among these secondary factors, and is itself sensitive to changes in hydroclimate. Leaf water enrichment also occurs prior to photosynthetic water uptake, and is therefore independent from cellular-level biomarker synthesis. Mechanistic models can predict the mean leaf water hydrogen isotope composition from readily available meteorological variables. This permits global-scale isoscape maps of leaf water isotopic composition and enrichment above source water to be generated, but these models have not been widely validated at continental spatial scales. We have established a network of twenty-one sites across Europe where we are sampling for leaf-, xylem-, and soil-water isotopes (H and O) at approximately 5-week intervals over the summer growing season. We augment the sample set with weekly to monthly precipitation samples and early- and late-season plant wax lipid samples. Collaborators at each site are conducting the sampling, and most sites are members of the FLUXNET tower network that also record high-resolution meteorological data. We present information on the implementation of the network and preliminary results from the 2014 summer season. The complete dataset will be used to track the evolution of water isotopes from source to leaf water and from leaf water to lipid hydrogen across diverse environments

  8. Stable hydrogen and oxygen isotope ratios of bottled waters of the world.

    PubMed

    Bowen, Gabriel J; Winter, David A; Spero, Howard J; Zierenberg, Robert A; Reeder, Mathew D; Cerling, Thure E; Ehleringer, James R

    2005-01-01

    Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential

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

    SciTech Connect

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

    1986-12-01

    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/sub 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/sup 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/sub 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/sub 2/ production.

  10. Hydrogen and oxygen isotope ratios in human hair are related to geography

    PubMed Central

    Ehleringer, James R.; Bowen, Gabriel J.; Chesson, Lesley A.; West, Adam G.; Podlesak, David W.; Cerling, Thure E.

    2008-01-01

    We develop and test a model to predict the geographic region-of-origin of humans based on the stable isotope composition of their scalp hair. This model incorporates exchangeable and nonexchangeable hydrogen and oxygen atoms in amino acids to predict the δ2H and δ18O values of scalp hair (primarily keratin). We evaluated model predictions with stable isotope analyses of human hair from 65 cities across the United States. The model, which predicts hair isotopic composition as a function of drinking water, bulk diet, and dietary protein isotope ratios, explains >85% of the observed variation and reproduces the observed slopes relating the isotopic composition of hair samples to that of local drinking water. Based on the geographical distributions of the isotope ratios of tap waters and the assumption of a “continental supermarket” dietary input, we constructed maps of the expected average H and O isotope ratios in human hair across the contiguous 48 states. Applications of this model and these observations are extensive and include detection of dietary information, reconstruction of historic movements of individuals, and provision of region-of-origin information for unidentified human remains. PMID:18299562

  11. Hydrogen and oxygen isotope ratios in human hair are related to geography.

    PubMed

    Ehleringer, James R; Bowen, Gabriel J; Chesson, Lesley A; West, Adam G; Podlesak, David W; Cerling, Thure E

    2008-02-26

    We develop and test a model to predict the geographic region-of-origin of humans based on the stable isotope composition of their scalp hair. This model incorporates exchangeable and nonexchangeable hydrogen and oxygen atoms in amino acids to predict the delta(2)H and delta(18)O values of scalp hair (primarily keratin). We evaluated model predictions with stable isotope analyses of human hair from 65 cities across the United States. The model, which predicts hair isotopic composition as a function of drinking water, bulk diet, and dietary protein isotope ratios, explains >85% of the observed variation and reproduces the observed slopes relating the isotopic composition of hair samples to that of local drinking water. Based on the geographical distributions of the isotope ratios of tap waters and the assumption of a "continental supermarket" dietary input, we constructed maps of the expected average H and O isotope ratios in human hair across the contiguous 48 states. Applications of this model and these observations are extensive and include detection of dietary information, reconstruction of historic movements of individuals, and provision of region-of-origin information for unidentified human remains.

  12. Automotive hydrogen storage system using cryo-adsorption on activated carbon.

    SciTech Connect

    Ahluwalia, R. K.; Peng, J. K.; Nuclear Engineering Division

    2009-07-01

    An integrated model of a sorbent-based cryogenic compressed hydrogen system is used to assess the prospect of meeting the near-term targets of 36 kg-H{sub 2}/m{sup 3} volumetric and 4.5 wt% gravimetric capacity for hydrogen-fueled vehicles. The model includes the thermodynamics of H{sub 2} sorption, heat transfer during adsorption and desorption, sorption dynamics, energetics of cryogenic tank cooling, and containment of H{sub 2} in geodesically wound carbon fiber tanks. The results from the model show that recoverable hydrogen, rather than excess or absolute adsorption, is a determining measure of whether a sorbent is a good candidate material for on-board storage of H{sub 2}. A temperature swing is needed to recover >80% of the sorption capacity of the superactivated carbon sorbent at 100 K and 100 bar as the tank is depressurized to 3-8 bar. The storage pressure at which the system needs to operate in order to approach the system capacity targets has been determined and compared with the breakeven pressure above which the storage tank is more compact if H{sub 2} is stored only as a cryo-compressed gas. The amount of liquid N{sub 2} needed to cool the hydrogen dispensed to the vehicle to 100 K and to remove the heat of adsorption during refueling has been estimated. The electrical energy needed to produce the requisite liquid N{sub 2} by air liquefaction is compared with the electrical energy needed to liquefy the same amount of H{sub 2} at a central plant. The alternate option of adiabatically refueling the sorbent tank with liquid H{sub 2} has been evaluated to determine the relationship between the storage temperature and the sustainable temperature swing. Finally, simulations have been run to estimate the increase in specific surface area and bulk density of medium needed to satisfy the system capacity targets with H{sub 2} storage at 100 bar.

  13. Hydrogen adsorption capacities of multi-walled boron nitride nanotubes and nanotube arrays: a grand canonical Monte Carlo study.

    PubMed

    Ahadi, Zohreh; Shadman, Muhammad; Yeganegi, Saeed; Asgari, Farid

    2012-07-01

    Hydrogen adsorption in multi-walled boron nitride nanotubes and their arrays was studied using grand canonical Monte Carlo simulation. The results show that hydrogen storage increases with tube diameter and the distance between the tubes in multi-walled boron nitride nanotube arrays. Also, triple-walled boron nitride nanotubes present the lowest level of hydrogen physisorption, double-walled boron nitride nanotubes adsorb hydrogen better when the diameter of the inner tube diameter is sufficiently large, and single-walled boron nitride nanotubes adsorb hydrogen well when the tube diameter is small enough. Boron nitride nanotube arrays adsorb hydrogen, but the percentage of adsorbed hydrogen (by weight) in boron nitride nanotube arrays is rather similar to that found in multi-walled boron nitride nanotubes. Also, when the Langmuir and Langmuir-Freundlich equations were fitted to the simulated data, it was found that multi-layer adsorptivity occurs more prominently as the number of walls and the tube diameter increase. However, in single-walled boron nitride nanotubes with a small diameter, the dominant mechanism is monolayer adsorptivity.

  14. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  15. Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials.

    PubMed

    Zhao, Xuebo; Villar-Rodil, Silvia; Fletcher, Ashleigh J; Thomas, K Mark

    2006-05-25

    Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.

  16. Hydrogen isotope systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis

    NASA Astrophysics Data System (ADS)

    Kobayashi, M.; Kawagucci, S.; Hattori, S.; Yamada, K.; Ueno, Y.; Takai, K.; Yoshida, N.

    2011-12-01

    Hydrogen and carbon isotopes of CH4 have been utilized to trace microbial processes. The isotope fractionations during hydrogenotrophic methanogenesis, one of the major processes of environmental CH4, have been studied by several laboratory incubations. For the carbon isotope, H2 concentration is thought to be the major parameter controlling the carbon isotope fractionation by hydrogenotrophic methanogenesis. For the hydrogen, on the other hand, factors controlling isotope fractionation remain poorly understood, although H2 concentration is suggested to be important. This uncertainty prevents us to utilize δD-CH4 value as the tracer. The most important and principal question is whether all hydrogen atoms in microbially-generated CH4 come from environmental H2O or not. To answer the question, we investigated the D/H systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis by pure culture incubation with softly deuterium-enriched H2 and/or H2O. Our results demonstrate that δD-CH4 value produced by hydrogenotrophic methanogens depends not only on δD-H2O value but also on δD-H2 value. We observed constant correlation between δD-H2 and δD-CH4 values as well as between δD-H2O and δD-CH4 values, which suggests that hydrogen (/deuterium) atom of substrate H2 is also transferred to the product CH4. This implies that the range of δD-CH4 value produced by hydrogenotrophic methanogenesis should be re-evaluated considering the distribution of δD-H2 and δD-H2O values in natural environments.

  17. Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal-organic framework.

    PubMed

    Yang, Sihai; Lin, Xiang; Blake, Alexander J; Walker, Gavin S; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2009-09-01

    Metal-organic frameworks (MOFs)--microporous materials constructed by bridging metal centres with organic ligands--show promise for applications in hydrogen storage, which is a key challenge in the development of the 'hydrogen economy'. Their adsorption capacities, however, have remained insufficient for practical applications, and thus strategies to enhance hydrogen-MOF interactions are required. Here we describe an anionic MOF material built from In(III) centres and tetracarboxylic acid ligands (H(4)L) in which kinetic trapping behaviour--where hydrogen is adsorbed at high pressures but not released immediately on lowering the pressure--is modulated by guest cations. With piperazinium dications in its pores, the framework exhibits hysteretic hydrogen adsorption. On exchange of these dications with lithium cations, no hysteresis is seen, but instead there is an enhanced adsorption capacity coupled to an increase in the isosteric heat of adsorption. This is rationalized by the different locations of the cations within the pores, determined with precision by X-ray crystallography.

  18. Neutron Diffraction Studies of Hydrogen Adsorption in a Highly Stable Porous Rare-Earth Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Luo, Junhua; Zhao, Yusheng; Xu, Hongwu; Daemen, Luc L.

    2008-10-01

    Gas sorption measurements show that a highly stable porous lanthanide metal-organic framework can take up hydrogen of about 2.1 wt. % at 77 K and 10 bar. Difference Fourier analysis of neutron powder diffraction data revealed four distinct D2 sites that are progressively filled within the nanoporous framework. Interestingly, the strongest adsorption sites identified are associated with the aromatic organic linkers rather than the open metal sites, as occurred in previously reported MOFs. Our results provide for the first time direct structural evidence demonstrating that optimal pore size (around 6 å, twice the kinetic diameter of hydrogen) strengthens the interactions between H2 molecules and pore walls and increases the heat of adsorption, which thus allows for enhancing hydrogen adsorption from the interaction between hydrogen molecules with the pore walls rather than with the normally stronger adsorption sites (the open metal sites) within the framework. At high concentration H2-loadings (5.5 H2 molecules (3.7 wt. %) per Y(BTC) formula), H2 molecules form highly symmetric novel nanoclusters with relatively short H2-H2 distances compared to solid H2. These observations are important and hold the key to optimizing this new class of rare metal-organic frameworks (RMOFs) materials for practical hydrogen storage applications.

  19. Using stable-hydrogen isotopes to reveal immigration in an Arctic-breeding songbird population.

    PubMed

    Bairlein, Franz; Norris, D Ryan; Voigt, Christian C; Dunn, Erica H; Hussell, David J T

    2016-01-01

    Knowledge of immigration and emigration rates is crucial for understanding of population dynamics, yet little is known about these vital rates, especially for arctic songbirds. We estimated immigration in an Arctic population of northern wheatears on Baffin Island, Canada, by the use of stable hydrogen isotopes in tail feathers (δ(2)HK). We assumed that δ(2)HK values of juvenile (hatch-year) feathers grown at the breeding grounds were representative of the local population, while those of breeding adults were indicative of where they grew their feathers during their post-breeding molt the previous year. The extent to which adult isotope values differ from those of juveniles provides an estimate of the minimum level of immigration into the breeding population. Mean δ(2)HK values did not differ in juvenile birds between years. Breeding adult birds did not differ significantly in mean δ(2)HK values compared to juveniles but did differ in their respective standard deviations, reflecting a significantly wider range of isotopic signatures in adults than in juveniles. Thirty-eight percent of the δ(2)HK values in adults were greater ± 2 SD of the mean δ(2)HK values of juveniles, suggesting that at least 38 % of the breeding adults were of non-local origin, thus immigrants from elsewhere. Although the use of stable isotopes has limitations, the use of stable-hydrogen isotopic markers has the potential to contribute valuable information towards understanding immigration rates in bird populations. In our study, hydrogen isotope measurements of the feathers of northern wheatears indicated a high rate of immigration into the breeding population, which is consistent with low return rates of banded breeding adults as well as implying high emigration rates of local breeders.

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

    PubMed Central

    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 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. PMID:27531993

  1. Mica Mountain Muscovite: A New Silicate Hydrogen Isotope Standard Reference Material

    NASA Astrophysics Data System (ADS)

    Lonero, A.; Larson, P. B.; Neill, O. K.

    2015-12-01

    A new standard reference material consisting of finely ground muscovite flakes has been developed and utilized at Washington State University to calibrate hydrogen isotope ratio (D/H) measurements to the VSMOW scale. This standard was prepared from a single crystal 'book' of a muscovite-bearing pegmatite near Deary, ID. The value we obtained for this muscovite standard (MMM) is: δD VSMOW = -79.1 ± 2.0‰ relative to NBS-30 biotite at -65.7‰ compared to a VSMOW value of 0.00‰. This mean value was determined for the muscovite and has been used as our working standard. There have been many recent geological applications to continuous flow isotope ratio mass spectroscopy. When hydrogen isotope ratios are of interest, a suitable standard for hydrogen in silicate systems often is not available. With supplies of the older NBS-30 biotite standard exhausted, much D/H data measured on silicate minerals have been linked to the VSMOW scale via non-silicate reference materials which may not behave similarly to minerals under study. Some recent studies have shown the NBS-30 standard to have poor intra-laboratory agreement with that material's measured and accepted isotopic values (Qi et al., 2014). Many laboratories which would measure D/H in silicate minerals would benefit from using a silicate-based standard for hydrogen. With further characterization, this muscovite may also be useful as a standard for silicate oxygen ratios as well as for some major element cations. This muscovite standard gives consistent values and it is easy to work with and does not leave much combustion residue. Also, because muscovite contains little iron, metal-hydride formation and associated fractionation factors is greatly reduced during the sample combustion. A new silicate-hydrogen standard is needed by the community, and this work represents an example of what a replacement standard material could look like.

  2. Hydrogen isotopes in Eocene river gravels and paleoelevation of the Sierra Nevada.

    PubMed

    Mulch, Andreas; Graham, Stephan A; Chamberlain, C Page

    2006-07-07

    We determine paleoelevation of the Sierra Nevada, California, by tracking the effect of topography on precipitation, as recorded in hydrogen isotopes of kaolinite exposed in gold-bearing river deposits from the Eocene Yuba River. The data, compared with the modern isotopic composition of precipitation, show that about 40 to 50 million years ago the Sierra Nevada stood tall (>/=2200 meters), a result in conflict with proposed young surface uplift by tectonic and climatic forcing but consistent with the Sierra Nevada representing the edge of a pre-Eocene continental plateau.

  3. Systematics of isotopic production cross sections from interactions of relativistic 40Ca in hydrogen

    NASA Astrophysics Data System (ADS)

    Chen, C.-X.; Albergo, S.; Caccia, Z.; Costa, S.; Crawford, H. J.; Cronqvist, M.; Engelage, J.; Greiner, L.; Guzik, T. G.; Insolia, A.; Knott, C. N.; Lindstrom, P. J.; McMahon, M.; Mitchell, J. W.; Potenza, R.; Russo, G. V.; Soutoul, A.; Testard, O.; Tull, C. E.; Tuvé, C.; Waddington, C. J.; Webber, W. R.; Wefel, J. P.

    1997-09-01

    The isotopic production cross sections for 40Ca projectiles at 357, 565, and 763 MeV/nucleon interacting in a liquid hydrogen target have been measured by the Transport Collaboration at the LBL HISS facility. The systematics of these cross sections are studied, and the results indicate that nuclear structure effects are present in the isotope production process during the relativistic collisions. The newly measured cross sections are also compared with those predicted by semiempirical and parametric formulas, but the predictions do not fully describe the systematics such as the energy dependence. The consequences of the cross section systematics in galactic cosmic ray studies are also discussed.

  4. Microscopic observation of kinetic molecular sieving of hydrogen isotopes in a nanoporous material.

    PubMed

    Nguyen, T X; Jobic, H; Bhatia, S K

    2010-08-20

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  5. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    NASA Astrophysics Data System (ADS)

    Nguyen, T. X.; Jobic, H.; Bhatia, S. K.

    2010-08-01

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  6. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    SciTech Connect

    Nguyen, T. X.; Bhatia, S. K.; Jobic, H.

    2010-08-20

    We report quasielastic neutron scattering studies of H{sub 2}-D{sub 2} diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  7. Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

    NASA Astrophysics Data System (ADS)

    Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

    2017-08-01

    Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

  8. Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

    USGS Publications Warehouse

    Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

    2008-01-01

    Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

  9. Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

    NASA Astrophysics Data System (ADS)

    Balistrieri, Laurie S.; Borrok, David M.; Wanty, Richard B.; Ridley, W. Ian

    2008-01-01

    Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (αsoln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δsoln-solid) are -0.73 ± 0.08‰ for Cu and -0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

  10. Oxygen and hydrogen isotope systematics of Lake Baikal, Siberia: Implications for paleoclimate studies

    USGS Publications Warehouse

    Seal, R.R.; Shanks, Wayne C.

    1998-01-01

    We interpret oxygen and hydrogen isotope data for water samples from Lake Baikal, Siberia, its tributaries and other local rivers, and local precipitation in terms of the known water budget for the modem lake in order to gain insight into past limnological and climatic processes that influenced the lake. Lake Baikal is remarkably uniform in its isotopic composition (??18O = -15.8 ?? 0.2???; ??D = -123 ?? 2???) and lies slightly to the right of the global meteoric water line, which suggests significant evaporation. Water is supplied to the lake by over 300 rivers and streams. The oxygen isotope values (??18O) of the rivers in the Baikal catchment range from -13.4 to -21.2???. The hydrogen isotope values (??D) for the same area range from -103 to -156???. Both these ranges generally conform to the global meteoric water line. The weighted average isotopic composition of input to the lake (rivers plus precipitation) is -15.2??? for ??18O and -116??? for ??D, values higher than those of the modem lake. Therefore, the isotopic composition of the modem lake cannot be related to the modem input through simple evaporation. Instead, modeling of the isotopic mass balance of the lake suggests that inputs (precipitation and influx from rivers) and outputs (evaporation and outflow) are not at a steady-state equilibrium under current climate conditions. We found previous input to the lake had lower ??18O and ??D values than modem input, which reflects cooler climates in the past compared with modern conditions. Under constant climate conditions, steady-state conditions are not expected to be reached by the lake for at least 700 yr because of its large size and the long residence time of water in the lake.

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

    PubMed

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

    2014-01-01

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

  12. Hydrogen Isotope Biogeochemistry of Plant Biomarkers in Tropical Trees from the Andes to Amazon

    NASA Astrophysics Data System (ADS)

    Feakins, S. J.; Ponton, C.; West, A. J.; Malhi, Y.; Goldsmith, G.; Salinas, N.; Bentley, L. P.

    2014-12-01

    Plant leaf waxes are well known biomarkers for terrestrial vegetation. Generally, their hydrogen isotopic composition (D/H) records the isotopic composition of precipitation, modulated by leaf water processes and a large biosynthetic fractionation. In addition, the D/H of methoxyl groups on tree wood lignin is an emerging technique thought to record the D/H of source waters, without leaf water complications. Using each of these biomarkers as proxies requires understanding D/H fractionations in plant systems, but few studies have directly studied hydrogen isotope biogeochemistry in tropical plants. An approach that has proven helpful is the paired analysis of plant waters and plant biomarkers: in order that fractionations can be directly computed rather than assumed. This presents logistical challenges in remote tropical forest environments. We report on a unique dataset collected by tree-climbers from 6 well-studied vegetation plots across a 4km elevation transect in the Peruvian Andes and Amazonia. We have measured the D/H of stem water and leaf water, and we compare these to precipitation isotopes and stream waters. The goal of the plant water studies is to understand plant water uptake and stem-leaf water isotopic offsets which can vary due to both transpiration and foliar uptake of water in tropical montane forests. We are in the process of measuring the D/H of plant biomarkers (n-alkanoic acids, n-alkanes and lignin methoxyl) in order to assess how these water isotopic signals are encoded in plant biomarkers. We compare the species-specific modern plant insights to the plant leaf wax n-alkanoic acid D/H that we have recently reported from soils and river sediments from the same region, in order to understand how signals of plant biogeochemistry are integrated into geological sedimentary archives. Progress and open questions in tropical isotope biogeochemistry will be discussed at the meeting.

  13. Isotopically exchangeable organic hydrogen in coal relates to thermal maturity and maceral composition

    USGS Publications Warehouse

    Mastalerz, Maria; Schimmelmann, A.

    2002-01-01

    Hydrogen isotopic exchangeability (Hex) and ??Dn values of non-exchangeable organic hydrogen were investigated in coal kerogens ranging in rank from lignite to graphite. The relative abundance of Hex is highest in lignite with about 18% of total hydrogen being exchangeable, and decreases to around 2.5% in coals with Ro of 1.7 to ca. 5.7%. At Still higher rank (Ro > 6%), Hex increases slightly, although the abundance of total hydrogen decreases. ??Dn is influenced by original biochemical D/H ratios and by thermal maturation in contact with water. Therefore, ??Dn does not show an overall consistent trend with maturity. ?? 2002 Elsevier Science Ltd. All rights reserved.

  14. FI-STM study of hydrogen adsorption on Si(100) surface

    NASA Astrophysics Data System (ADS)

    Hua, Lu; Xiang-dong, Wang; Motai, K.; Hashizume, T.; Sakurai, T.

    1992-11-01

    Chemisorption of atomic hydrogen on the Si(100)2 × 1 surface has been investigated in detail by using a field ion-scanning tunneling microscope (FI-STM). The results showed that the adsorption geometry changed from the 2 × 1 monohydride phase to the 1 × 1 dihydride phase with increasing exposure of hydrogen. The data of desorption of the hydrogen-saturated Si surface showed that on annealing at 670 K the surface becomes highly disordered: the 1 × 1 dihydride structure is eliminated and the 2 × 1 reconstructed monohydride is also hardly to identify. When the temperature rises to as high as 730 K, the surface is dominated by the 2 × 1 structure with missing dimer rows, and some adatom chains occur on the Si substrate terraces. We attribute the formation of these atomic chains to an epitaxial growth of Si atoms which are formed by the dissociation of SiHx (x = 1, 2, 3 or 4) compounds on the Si surface.

  15. Adsorption, diffusion, and recombination of hydrogen on pure and boron-doped graphite surfaces.

    PubMed

    Ferro, Y; Marinelli, F; Jelea, A; Allouche, A

    2004-06-22

    Boron inserted as impurity by substitution of carbon atoms in graphite is known to modify the reactivity of the surface in interaction with hydrogen. Boron induces a better H retention capability in graphite while it makes easier the recombination into molecular hydrogen under heating in thermal-desorption experimental conditions. It has already been calculated that boron modifies the electronic structure of the surface, which results in an increase of the adsorption energy for H. This result seems in good agreement with the better retention for H in doped graphite, but contradictory with the easier recombination observed. The aim of this work is to dismiss this contradiction by elucidating the modifications induced by boron in the recombination mechanism. We studied the diffusion of H on pure and boron-doped graphite in the density functional theory framework. We determined a diffusionlike mechanism leading to molecular hydrogen formation. Finally, we have shown the fundamental modifications induced by boron on the [0001] graphite surface reactivity. From these calculations it stands out that recombination is the result of desorption on pure graphite and diffusion on B-doped surfaces, while the activation energy for the rate limiting step is half reduced by boron. The results are compared to experimental observations. The connection between the cluster and periodic quantum modes for graphite is also discussed. (c) 2004 American Institute of Physics.

  16. CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Adsorption Mechanism of Hydrogen on Boron-Doped Fullerenes

    NASA Astrophysics Data System (ADS)

    Yu, Liu-Min; Shi, Guo-Sheng; Wang, Zhi-Gang; Ji, Guang-Fu; Lu, Zhi-Peng

    2009-08-01

    The C35BH-H2 complex and two other possible isomers, C34BCaH-H2 and C34BCbH-H2, are investigated using the local-spin-density approximation (LSDA) method. The results indicate that a single hydrogen molecule could be strongly adsorbed on two isomers, C34BCaH and C34BCbH, with binding energies of 0.42 and 0.47 eV, respectively, and that these calculated binding energies are suitable for reversible hydrogen adsorption/desorption near room temperature. However, it is difficult for the H2 molecule to be firmly adsorbed on C35BH. We analyze the interaction between C34BCxH (x = a, b) and the H2 molecule using dipole moments and molecular orbitals. The charge analysis showed there was a partial charge (about 0.32e) transfer from H2 to the doped fullerenes. These calculation results should broaden our understanding of the mechanisms of hydrogen storage using boron-doped fullerenes.

  17. HYDROGEN ISOTOPE RECOVERY USING PROTON EXCHANGE MEMBRANE ELECTROLYSIS OF WATER

    SciTech Connect

    Fox, E; Scott Greenway, S; Amy Ekechukwu, A

    2007-08-27

    A critical component of tritium glovebox operations is the recovery of high value tritium from the water vapor in the glove box atmosphere. One proposed method to improve existing tritium recovery systems is to replace the disposable hot magnesium beds used to separate the hydrogen and oxygen in water with continuous use Proton Exchange Membrane Electrolyzers (PEMEs). This study examines radiation exposure to the membrane of a PEME and examines the sizing difference that would be needed if the electrolyzer were operated with a cathode water vapor feed instead of an anode liquid water feed.

  18. Vibrational Spectroscopic Studies of Hydrogen, Carbon-Monoxide and Thiophene Adsorption on Ruthenium-Sulfide and Sulfided Ruthenium Catalysts.

    NASA Astrophysics Data System (ADS)

    Heise, William Herbert

    The "working surface" of ruthenium hydrodesulfurization (HDS) catalysts has been modeled by preadsorption of sulfur, carbon and carbon plus sulfur on Ru(0001). Adsorption and decomposition of thiophene over these surfaces have been investigated using TDS/TPRS, XPS and EELS. Thiophene is proposed to decompose via a three-step mechanism involving: (i) initial thiophene cracking at 120 K yielding surface sulfur and hydrocarbon species, (ii) hydrogen desorption near 230 K providing additional decomposition ensembles and (iii) continued decomposition to form "metallocycle -like" intermediates which retain EELS features similar to thiophene. Preadsorbed carbon or carbon plus sulfur are not as effective for passivation of the surface toward metallocycle formation as preadsorbed sulfur alone. This result is attributed to the fact that carbon deposited from butadiene annealed and decomposed at 700 K forms islands, while sulfur establishes a well-ordered superlattice on the surface. The decrease in metallocycle formation with increasing poison levels appears to explain HDS selectivity and specific activity trends observed in our laboratory from mildly sulfided (10% H_2S/H_2 , 673 K, 2h) ruthenium catalysts retaining submonolayers of sulfur. Incoherent inelastic neutron scattering (IINS) has been used to characterize hydrogen adsorption sites on ruthenium sulfide. Hydrogen resides on sulfur anions to form SH groups, yielding two non-degenerate bending modes at 600 and 710 cm^{-1}. Complementary hydrogen adsorption and H_2/D _2 exchange data suggest that the active sites for hydrogen adsorption may be coordinatively unsaturated S-S anion pairs. Comparison of CO adsorption on sulfided Ru/Al _2O_3 to sulfur precovered Ru(0001) reveals an adsorption site related to edge/corner atoms directly perturbed by sulfur, consistent with previous kinetic studies demonstrating higher specific activity for thiophene HDS over smaller ruthenium crystallites.

  19. Direct observation and modelling of ordered hydrogen adsorption and catalyzed ortho-para conversion on ETS-10 titanosilicate material.

    PubMed

    Ricchiardi, Gabriele; Vitillo, Jenny G; Cocina, Donato; Gribov, Evgueni N; Zecchina, Adriano

    2007-06-07

    Hydrogen physisorption on porous high surface materials is investigated for the purpose of hydrogen storage and hydrogen separation, because of its simplicity and intrinsic reversibility. For these purposes, the understanding of the binding of dihydrogen to materials, of the structure of the adsorbed phase and of the ortho-para conversion during thermal and pressure cycles are crucial for the development of new hydrogen adsorbents. We report the direct observation by IR spectroscopic methods of structured hydrogen adsorption on a porous titanosilicate (ETS-10), with resolution of the kinetics of the ortho-para transition, and an interpretation of the structure of the adsorbed phase based on classical atomistic simulations. Distinct infrared signals of o- and p-H2 in different adsorbed states are measured, and the conversion of o- to p-H2 is monitored over a timescale of hours, indicating the presence of a catalyzed reaction. Hydrogen adsorption occurs in three different regimes characterized by well separated IR manifestations: at low pressures ordered 1:1 adducts with Na and K ions exposed in the channels of the material are formed, which gradually convert into ordered 2:1 adducts. Further addition of H2 occurs only through the formation of a disordered condensed phase. The binding enthalpy of the Na+-H2 1:1 adduct is of -8.7+/-0.1 kJ mol(-1), as measured spectroscopically. Modeling of the weak interaction of H2 with the materials requires an accurate force field with a precise description of both dispersion and electrostatics. A novel three body force field for molecular hydrogen is presented, based on the fitting of an accurate PES for the H2-H2 interaction to the experimental dipole polarizability and quadrupole moment. Molecular mechanics simulations of hydrogen adsorption at different coverages confirm the three regimes of adsorption and the structure of the adsorbed phase.

  20. An analytical system for the measurement of stable hydrogen isotopes in ambient volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, T.; Bühler, F.; Koppmann, R.; Krebsbach, M.

    2015-10-01

    Stable isotope measurements in atmospheric volatile organic compounds (VOCs) are an excellent tool to analyse chemical and dynamical processes in the atmosphere. While up to now isotope studies of VOCs in ambient air have mainly focussed on carbon isotopes, we herein present a new measurement system to investigate hydrogen isotope ratios in atmospheric VOCs. This system, consisting of a gas chromatography pyrolysis isotope ratio mass spectrometer (GC-P-IRMS) and a pre-concentration system, was thoroughly characterised using a VOC test mixture. A precision of better than 9 ‰ (in δ 2H) is achieved for n-pentane, 2-methyl-1,3-butadiene (isoprene), n-heptane, 4-methyl-pentane-2-one (4-methyl-2-pentanone), methylbenzene (toluene), n-octane, ethylbenzene, m/p-xylene and 1,2,4-trimethylbenzene. A comparison with independent measurements via elemental analysis shows an accuracy of better than 9 ‰ for n-pentane, n-heptane, 4-methyl-2-pentanone, toluene and n-octane. Above a minimum required pre-concentrated compound mass the obtained δ 2H values are constant within the standard deviations. In addition, a remarkable influence of the pyrolysis process on the isotope ratios is found and discussed. Reliable measurements are only possible if the ceramic tube used for the pyrolysis is sufficiently conditioned, i.e. the inner surface is covered with a carbon layer. It is essential to verify this conditioning regularly and to renew it if required. Furthermore, influences of a necessary H3+ correction and the pyrolysis temperature on the isotope ratios are discussed. Finally, the applicability to measure hydrogen isotope ratios in VOCs at ambient levels is demonstrated with measurements of outside air on 5 different days in February and March 2015. The measured hydrogen isotope ratios range from -136 to -105 ‰ forn-pentane, from -86 to -63 ‰ for toluene, from -39 to -15 ‰ for ethylbenzene, from -99 to -68 ‰ for m/p-xylene and from -45 to -34 ‰ for o-xylene.

  1. An analytical system for the measurement of stable hydrogen isotopes in ambient volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, T.; Bühler, F.; Koppmann, R.; Krebsbach, M.

    2015-07-01

    Stable isotope measurements in atmospheric volatile organic compounds (VOC) are an excellent tool to analyse chemical and dynamical processes in the atmosphere. While up to now isotope studies of VOC in ambient air mainly focus on carbon isotopes, we herein present a new measurement system to investigate hydrogen isotope ratios in atmospheric VOC. This system consisting of a GC-P-IRMS (Gas Chromatography Pyrolysis Isotope Ratio Mass Spectrometer) and a preconcentration system was thoroughly characterised using a working standard. A precision of better than 9 ‰ (in δD) is achieved for n-pentane, 2-methyl-1,3-butadiene (isoprene), n-heptane, 4-methyl-pentane-2-one (4-methyl-2-pentanone), methylbenzene (toluene), n-octane, ethylbenzene, m/p-xylene, and 1,2,4-trimethylbenzene. A comparison with independent measurements via elemental analysis shows an accuracy of better than 9 ‰ for n-pentane, n-heptane, 4-methyl-2-pentanone, toluene, and n-octane. Above a compound specific minimum peak area the obtained δD values are constant within the standard deviations. In addition, a remarkable influence of the pyrolysis process on the isotope ratios is found and discussed. Reliable measurements are only possible if the ceramic tube used for the pyrolysis is sufficiently conditioned, i.e. the inner surface is covered with a carbon layer. It is essential to verify this conditioning regularly and to renew it if required. Furthermore, influences of a necessary H3+ correction and the pyrolysis temperature on the isotope ratios are discussed. Finally, the applicability to measure hydrogen isotope ratios in VOC at ambient levels is demonstrated with measurements of outside air on five different days in February and March 2015. The measured hydrogen isotope ratios range from -136 to -105 ‰ for n-pentane, from -86 to -63 ‰ for toluene, from -39 to -15 ‰ for ethylbenzene, from -99 to -68 ‰ for m/p-xylene, and from -45 to -34 ‰ for o-xylene.

  2. Thermochemical sulphate reduction (TSR) versus maturation and their effects on hydrogen stable isotopes of very dry alkane gases

    NASA Astrophysics Data System (ADS)

    Liu, Q. Y.; Worden, R. H.; Jin, Z. J.; Liu, W. H.; Li, J.; Gao, B.; Zhang, D. W.; Hu, A. P.; Yang, C.

    2014-07-01

    Here we report the first study of the effect of thermochemical sulphate reduction (TSR) on the hydrogen isotopes of natural gas. Variably sour (H2S-bearing) and very dry (>97% methane) gas samples from Lower Triassic, Permian and Carboniferous marine carbonate reservoirs in the Sichuan Basin, China, have been analysed. All gases seem to have been sourced from mature marine kerogen and contain H2S that resulted from TSR. The Carboniferous samples are largely unaffected by TSR and were used to assess the effects of normal thermal maturation processes on the carbon and hydrogen isotopes of methane and ethane as a function of gas dryness (a proxy for thermal maturity). Maturation led to heavier carbon isotopes of methane and ethane and hydrogen isotopes of ethane; in contrast methane hydrogen isotopes seem to have little systematic variation with increasing maturity. TSR did not have a systematic effect on the hydrogen isotopes of methane, although the spread of values diminished (ending up at a constant -120‰) as TSR proceeded. This was possibly due to the partial thermochemical sulphate reduction of ethane adding isotopically light methane and thus offsetting the Rayleigh fractionation effects of TSR of methane. In contrast, hydrogen isotopes of ethane became much heavier as TSR proceeded, to values greater than those for samples only influenced by maturation. Under some circumstances, the effects of TSR can be identified and discerned from the effects of normal thermal maturation by plotting the difference between the carbon isotope compositions of methane and ethane and the difference between the hydrogen isotope compositions of methane and ethane. Do the hydrogen isotope ratios of alkane gases systematically vary as a function of dryness or sourness? Do the hydrogen isotope ratios of alkane gases from the Carboniferous, Permian and Lower Triassic dry gas reservoirs help reveal the maturity and/or extent of TSR in the Sichuan Basin? Is it possible to separate and

  3. Hydrogen adsorption and mass flow on aluminum surfaces: Combined STM-infrared study

    NASA Astrophysics Data System (ADS)

    Go, Eden Parreno

    The influence of chemical adsorbates on surfaces is an important aspect of interface stability and chemical reactivity. This thesis addresses the adsorption properties of H and its effects on the equilibrium and dynamical properties on Al(111) surfaces. Using a combination of scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy (IRRAS) as probes, I observe dramatic changes in the surface morphology that occur upon hydrogen adsorption. I determine that gaseous H reacts directly with the surface by extracting surface atoms and initiates the formation of mobile ad-Al-H species that undergo a sequence of condensation and etching reactions to form molecular alanes that range from monomer to 30-mers in size. From IRRAS measurements, I establish the aluminum-hydrogen speciation as a function of coverage. Following adsorption, H preferentially occupies atop sites along the step edge, thereby modifying the properties of crystallographic steps. Using STM, I determine the influence of submonolayer coverages of H on the stability and kinetics of steps on Al(111) at room temperature. I determine that H raises the mobility of steps on the surface by lowering the kink and adatom formation energies. To determine the dominant mass transport at the step edge near equilibrium, I quantify the step fluctuation by employing the Langevin formalism. From the statistical analysis of step fluctuations, I deduce that the kink diffusion is the dominant mass transport mechanism at the step edge on the clean surface. Upon the adsorption of H, I determine that H amplifies the fluctuation of steps on Al(111) and propose a mechanism for H-induced step motion. Finally, I show that contrast in the STM images of molecular alanes is dependent on the chemical composition of the STM tip apex. Surface alanes are imaged as protrusions with a metallic W tip, but as depressions with an alane-terminated W tip. I observe that the change in contrast in the STM images is

  4. Hydrogen isotope discrimination in higher plants: Correlations with photosynthetic pathway and environment.

    PubMed

    Ziegler, H; Osmond, C B; Stichler, W; Trimborn, P

    1976-01-01

    The ratio of deuterium to hydrogen (expressed as δD) in hydrogen released as water during the combustion of dried plant material was examined. The δD value (metabolic hydrogen) determined on plant materials grown under controlled conditions is correlated with pathways of photosynthetic carbon metabolism. C3 plants show mean δD values of-132‰ for shoots and -117‰ for roots; C4 plants show mean δD values of -91‰ for shoots and-77‰ for roots and CAM plants a δD value of-75‰ for roots and shoots. The difference between the δD value of shoot material from C3 and C4 plants was confirmed in species growing under a range of glasshouse conditions. This difference in δD value between C3 and C4 species does not appear to be due to differences in the δD value (tissue water) in the plants as a result of physical fractionation of hydrogen isotopes during transpiration. In C3 and C4 plants the hydrogen isotope discrimination is in the same direction as the carbon isotope discrimination and factors contributing to the difference in δD values are discussed. In CAM plants grown in the laboratory or collected from the field δD values range from-75‰ to +50‰ and are correlated with δ(13)C values. When deprived of water, the δD value (metabolic hydrogen) in both soluble and insoluble material in leaves of Kalanchoe daigremontiana Hamet et Perr., becomes less negative. These changes may reflect the deuterium enrichment of tissue water during transpiration, or in field conditions, may reflect the different δD value of available water in areas of increasing aridity. Whatever the origin of the variable δD value in CAM plants, this parameter may be a useful index of the water relations of these plants under natural conditions.

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

    USGS Publications Warehouse

    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.

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

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2016-09-01

    The hydrogen isotopic composition (δ(2)HVSMOW-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 δ(2)HVSMOW-SLAP results 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 δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

  7. Assessment of renal function by the stable oxygen and hydrogen isotopes in human blood plasma.

    PubMed

    Kuo, Tai-Chih; Wang, Chung-Ho; Lin, Hsiu-Chen; Lin, Yuan-Hau; Lin, Matthew; Lin, Chun-Mao; Kuo, Hsien-Shou

    2012-01-01

    Water (H(2)O) is the most abundant and important molecule of life. Natural water contains small amount of heavy isotopes. Previously, few animal model studies have shown that the isotopic composition of body water could play important roles in physiology and pathophysiology. Here we study the stable isotopic ratios of hydrogen (δ(2)H) and oxygen (δ(18)O) in human blood plasma. The stable isotopic ratio is defined and determined by δ(sample) = [(R(sample)/R(STD))-1] * 1000, where R is the molar ratio of rare to abundant, for example, (18)O/(16)O. We observe that the δ(2)H and the δ(18)O in human blood plasma are associated with the human renal functions. The water isotope ratios of the δ(2)H and δ(18)O in human blood plasma of the control subjects are comparable to those of the diabetes subjects (with healthy kidney), but are statistically higher than those of the end stage renal disease subjects (p<0.001 for both ANOVA and Student's t-test). In addition, our data indicate the existence of the biological homeostasis of water isotopes in all subjects, except the end stage renal disease subjects under the haemodialysis treatment. Furthermore, the unexpected water contents (δ(2)H and δ(18)O) in blood plasma of body water may shed light on a novel assessment of renal functions.

  8. Assessment of Renal Function by the Stable Oxygen and Hydrogen Isotopes in Human Blood Plasma

    PubMed Central

    Kuo, Tai-Chih; Wang, Chung-Ho; Lin, Hsiu-Chen; Lin, Yuan-Hau; Lin, Matthew; Lin, Chun-Mao; Kuo, Hsien-Shou

    2012-01-01

    Water (H2O) is the most abundant and important molecule of life. Natural water contains small amount of heavy isotopes. Previously, few animal model studies have shown that the isotopic composition of body water could play important roles in physiology and pathophysiology. Here we study the stable isotopic ratios of hydrogen (δ2H) and oxygen (δ18O) in human blood plasma. The stable isotopic ratio is defined and determined by δsample = [(Rsample/RSTD)−1] * 1000, where R is the molar ratio of rare to abundant, for example, 18O/16O. We observe that the δ2H and the δ18O in human blood plasma are associated with the human renal functions. The water isotope ratios of the δ2H and δ18O in human blood plasma of the control subjects are comparable to those of the diabetes subjects (with healthy kidney), but are statistically higher than those of the end stage renal disease subjects (p<0.001 for both ANOVA and Student's t-test). In addition, our data indicate the existence of the biological homeostasis of water isotopes in all subjects, except the end stage renal disease subjects under the haemodialysis treatment. Furthermore, the unexpected water contents (δ2H and δ18O) in blood plasma of body water may shed light on a novel assessment of renal functions. PMID:22348150

  9. Carbon, Hydrogen and Chlorine Stable Isotope Fingerprinting for Forensic Investigations of Hexachlorocyclohexanes.

    PubMed

    Ivdra, Natalija; Fischer, Anko; Herrero-Martin, Sara; Giunta, Thomas; Bonifacie, Magali; Richnow, Hans-Hermann

    2017-01-03

    Multielemental stable isotope analysis of persistent organic pollutants (POPs) has the potential to characterize sources, sinks, and degradation processes in the environment. To verify the applicability of this approach for source identification of hexachlorocyclohexane (HCHs), we provide a data set of carbon, hydrogen, and chlorine stable isotope ratios (δ(13)C, δ(2)H, δ(37)Cl) of its main stereoisomers (α-, β-, δ- and γ-HCHs) from a sample collection based on worldwide manufacturing. This sample collection comprises production stocks, agricultural and pharmaceutical products, chemical waste dumps, and analytical-grade material, covering the production time period from the late 1960s until now. Stable isotope ratios of HCHs cover the ranges from -233‰ to +1‰, from -35.9‰ to -22.7‰, and from -6.69‰ to +0.54‰ for δ(2)H, δ(13)C, and δ(37)Cl values, respectively. Four groups of samples with distinct multielemental stable isotope fingerprints were differentiated, most probably as a result of purification and isolation processes. No clear temporal trend in the isotope compositions of HCHs was found at the global scale. The multielemental stable isotope fingerprints facilitate the source identification of HCHs at the regional scale and can be used to assess transformation processes. The data set and methodology reported herein provide basic information for the assessment of environmental field sites contaminated with HCHs.

  10. Hydrogen isotope variability in prairie wetland systems: implications for studies of migratory connectivity.

    PubMed

    Bortolotti, Lauren E; Clark, Robert G; Wassenaar, Leonard I

    2013-01-01

    Hydrogen isotopes (delta2H) are often used to infer the origins of migratory animals based on the strong correlation between deuterium content of tissues and long-term patterns of precipitation. However, the extreme flood and drought dynamics of surface waters in prairie wetland systems could mask these expected correlations. We investigated H isotopic variability in an aquatic food web associated with Tree Swallows (Tachycineta bicolor) that rely heavily on wetland-derived aerial insects for food. We evaluated isotopic turnover and incorporation of environmental water into tissue, processes that could affect H isotopic composition. Wetland water and aquatic invertebrates showed intra- and interannual H isotopic variation mainly related to evaporation and the amount and timing of precipitation. Snails showed rapid turnover of tissue deuterium and a large contribution of environmental water to their tissues. Swallow feather deuterium (delta2Hf) was variable but did not clearly follow changes in any of the food web compartments measured. Instead, isotopic variability may have been driven by shifts in the type or relative amounts of grey consumed and types of wetlands used. Nevertheless, despite relatively high variance in delta2Hf, the majority of birds fell within the predicted range of delta2Hf for the study area, revealing that significant trophic averaging occurred. However, both (presumed) diet shifts and variable hydrological conditions have the potential to greatly increase variance that must be considered when assigning origins of migratory animals based on delta2H.

  11. Experimental evidence for hydrogen tunneling when the isotopic arrhenius prefactor (A(H)/A(D)) is unity.

    PubMed

    Sharma, Sudhir C; Klinman, Judith P

    2008-12-31

    The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (A(H)/A(D)) of unity are generally ascribed to a semiclassical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an A(H)/A(D) of unity and highly elevated (nonclassical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semiclassical model based solely on an Arrhenius prefactor ratio.

  12. Effects of hydrogen adsorption on the properties of double wall BN and (BN)xCy nanotubes

    NASA Astrophysics Data System (ADS)

    Freitas, A.; Azevedo, S.; Kaschny, J. R.

    2016-01-01

    In the present contribution, we apply first-principles calculations, based on the density functional theory, to study the effects of hydrogen adsorption on the structural and electronic properties of boron nitride and hybrid carbon-boron nitride double wall nanotubes. The results demonstrate that the hydrogen decoration induces significant structural deformation and an appreciable reduction in the gap energy. When the number of hydrogen atoms introduced on the outer wall is increased, desorption of hydrogen pairs are observed. The calculations indicate that each adsorbed hydrogen atom induces a structural deformation with an energetic cost of about 68 meV/atom. It is also found that the introduction of hydrogen atoms can be applied as an efficient tool for tuning the electronic properties of such structures.

  13. Method and apparatus for storing hydrogen isotopes. [stored as uranium hydride in a block of copper

    DOEpatents

    McMullen, J.W.; Wheeler, M.G.; Cullingford, H.S.; Sherman, R.H.

    1982-08-10

    An improved method and apparatus for storing isotopes of hydrogen (especially tritium) are provided. The hydrogen gas is stored as hydrides of material (for example uranium) within boreholes in a block of copper. The mass of the block is critically important to the operation, as is the selection of copper, because no cooling pipes are used. Because no cooling pipes are used, there can be no failure due to cooling pipes. And because copper is used instead of stainless steel, a significantly higher temperature can be reached before the eutectic formation of uranium with copper occurs, (the eutectic of uranium with the iron in stainless steel forms at a significantly lower temperature).

  14. Precision Measurement of the Hydrogen-Deuterium 1S-2S Isotope Shift

    SciTech Connect

    Parthey, Christian G.; Matveev, Arthur; Alnis, Janis; Pohl, Randolf; Udem, Thomas; Kolachevsky, Nikolai; Haensch, Theodor W.; Jentschura, Ulrich D.

    2010-06-11

    Measuring the hydrogen-deuterium isotope shift via two-photon spectroscopy of the 1S-2S transition, we obtain 670 994 334 606(15) Hz. This is a 10-times improvement over the previous best measurement [A. Huber et al., Phys. Rev. Lett. 80, 468 (1998)] confirming its frequency value. A calculation of the difference of the mean square charge radii of deuterium and hydrogen results in {sub d}-{sub p}=3.820 07(65) fm{sup 2}, a more than twofold improvement compared to the former value.

  15. Hydrogen bonding and vapor pressure isotope effect of deuterioisomeric methanethiols

    SciTech Connect

    Wolff, H.; Szydlowski, J.; Dill-Staffenberger, L.

    1981-04-16

    Wilson parameters, activity coefficients, association constants, and other thermodynamic functions which are derived from isothermal vapor pressure measurements between 223 and 293 K for binary mixtures of CH/sub 3/SH, CH/sub 3/SD, CS/sub 3/SH, and CD/sub 3/SD with n-hexane show the weakness of the hydrogen and the deuterium bonds of methanethiol. As far as these functions depend on the association model used for the calculation, the relation of their values to those obtained for the corresponding amines and alcohols under the same conditions attests the weak methanethiol association. While for the more strongly associated methylamines and methanols a greater energy of the deuterium bond compared to the hydrogen bond has clearly been observed, the differences between the thermodynamic functions of the systems with the SH compounds and of those with the SD compounds are insignificant. This observation as well as the fact that the vapor pressure ratios P-(CH/sub 3/SD)/P(CH/sub 3/SH) are only slightly greater than unity, that the ratios P(CD/sub 3/SD)/P(CH/sub 3/SH) are even greater than P(CD/sub 3/SH)/P(CH/sub 3/SH), and that the changes of these ratios with temperature and dilution are small in comparison to the strong increase of the corresponding quotients of the methylamines and the methanols are the consequence of the weak methanethiol association. P(CH/sub 3/SD)/P(CH/sub 3/SH), P(CD/sub 3/SH)/P(CH/sub 3/SH), and P(CD/sub 3/SD)/P(CH/sub 3/SH) are represented by equations of the type ln P/sub D/ P/sub H/ = -A/T/sup 2/ + B/T where A and B are nearly additive. The low values of A and B for CH/sub 3/SD/CH/sub 3/SH in comparison to the high values for CH/sub 3/ND/sub 2//CH/sub 3/NH/sub 2/ and CH/sub 3/OD/CH/sub 3/OH reflect the weakness of the methanethiol hydrogen bonds. The constants can be related to the thermochemical and the spectroscopic data reported in the literature.

  16. INSTRUMENTS AND METHODS OF INVESTIGATION: Dynamic compression of hydrogen isotopes at megabar pressures

    NASA Astrophysics Data System (ADS)

    Trunin, Ryurik F.; Urlin, Vitalii D.; Medvedev, Aleksandr B.

    2010-09-01

    We review the results of shock compression of solid protium to the pressure 66 GPa, of liquid deuterium to 110 GPa, and of solid deuterium to 123 GPa in explosive devices of spherical geometry. The results are compared with data obtained by US scientists using traditional energy sources (explosives and light-gas guns), striker acceleration in a strong magnetic field (Z facility at Sandia), and powerful lasers (Nova at Lawrence Livermore National Laboratory (LLNL) and Omega at the Laboratory for Laser Energetics, University of Rochester). Results of density measurements of hydrogen isotopes under quasi-isentropic compression are analyzed. The absence of an anomalous increase in density under shock and quasi-isentropic compression of hydrogen isotopes is demonstrated. On the other hand, both processes exhibit a sharp change in the compression curve slopes, at the respective pressures 45 and 300 GPa.

  17. A Search for Heavy Hydrogen Isotopes in Cosmic-Ray Atmospheric Albedo With SAMPEX/PET

    NASA Astrophysics Data System (ADS)

    Looper, M. D.; Blake, J. B.; Mewaldt, R. A.

    2008-12-01

    Bidoli et al. (2003) reported observations of large abundances of deuterium and tritium relative to hydrogen below a few tens of MeV/nuc among the secondary particles escaping the atmosphere after the impact of primary cosmic rays. The SAMPEX satellite spent much of 1996-1998 spinning at 1 RPM, and since late 2007 it has been back in 1 RPM spin mode again; thus its sensors spend half their time looking downward, allowing atmospheric albedo particles to be observed directly. With the Proton/Electron Telescope (PET), hydrogen isotopes are measured in the energy range from about 18 MeV/nuc to 60 to 500 MeV/nuc depending on species. We have previously used PET to measure deuterium and tritium among the Earth's geomagnetically-trapped particle population; we will report here on the results of a search for these isotopes among atmospheric albedo during solar-activity minimum conditions.

  18. Isotopic hydrogen analysis via conventional and surface-enhanced fiber optic Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lascola, Robert; Zeigler, Kristine E.; McWhorter, C. Scott; Villa-Aleman, Eliel; Tovo, Laura L.; Ward, April E.

    2004-12-01

    This report describes laboratory development and process plant applications of Raman spectroscopy for detection of hydrogen isotopes in the Tritium Facilities at the Savannah River Site (SRS), a U.S. Department of Energy complex. Raman spectroscopy provides a lower-cost, in situ alternative to mass spectrometry techniques currently employed at SRS. Using conventional Raman and fiber optics, we have measured, in the production facility glove boxes, process mixtures of protium and deuterium at various compositions and total pressures ranging from 1000 - 4000 torr, with detection limits ranging from 1-2% for as low as 3-second integration times. We are currently investigating fabrication techniques for SERS surfaces in order to measure trace (0.01-0.1%) amounts of one isotope in the presence of the other. These efforts have concentrated on surfaces containing palladium, which promotes hydrogen dissociation and forms metal hydride bonds, essentially providing a chemical enhancement mechanism.

  19. Concentration of isotopic hydrogen by temperature gradient effect in soluble metal

    SciTech Connect

    Uhm, H.S.; Lee, W.W.

    1991-01-01

    This invention relates to the enrichment of isotopic hydrogen in a solid-state metal by use of temperature gradient effects, and is related to the subject matter disclosed in prior copending application Serial No. 07/724,083, filed July 1, 1991. High concentration of isotopic hydrogen in the form of deuterium atoms in a soluble metal such as palladium, is very useful for various electro-chemical studies including nuclear fusion investigations. A conventional technique used for deuterium enrichment purposes involves electrolysis, where a palladium rod is immersed in heavy water as the cathode. According to the prior copending application, aforementioned, deuterium density inside a palladium rod is increased by making use of plasma ion implantation. Patent Applications.

  20. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

    SciTech Connect

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; Bartynski, Robert A.

    2013-06-03

    Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.

  1. COMMENTS ON ANOMALOUS EFFECTS IN CHARGING OF PD POWDERS WITH HIGH DENSITY HYDROGEN ISOTOPES

    SciTech Connect

    Shanahan, K.

    2009-10-01

    In Kitamura, et al, Pd-containing materials are exposed to isotopes of hydrogen and anomalous results obtained. These are claimed to be a replication of another experiment conducted by Arata and Zhang. Erroneous basic assumptions are pointed out herein that alter the derived conclusions significantly. The final conclusion is that the reported results are likely normal chemistry combined with noise. Thus the claim to have proven that cold fusion is occurring in these systems is both premature and unlikely.

  2. Hydrogen Isotopes Record the History of the Martian Hydrosphere and Atmosphere

    NASA Technical Reports Server (NTRS)

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

    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. This study presents insights from hydrogen isotopes for the origin and evolution of Martian water reservoirs.

  3. 35Cl NQR study of geometric isotope effect in hydrogen bonded chlorooctanes

    NASA Astrophysics Data System (ADS)

    Zdanowska-Fraçzek, M.

    1994-05-01

    35Cl NQR spectroscopy was applied to study the geometric isotope effect in a wide range of 2 : 1 salts of chloroacetic, trichloroacetic and difluorochloroacetic acids. The NQR results were correlated with IR spectroscopic studies, which provided information on the potential shape for proton motion. The NQR results were discussed on the basis of a variational correlated ground state wave function theory of a single hydrogen bond.

  4. Multi-purpose hydrogen isotopes separation plant design

    SciTech Connect

    Boniface, H.A.; Gnanapragasam, N.V.; Ryland, D.K.; Suppiah, S.; Castillo, I.

    2015-03-15

    There is a potential interest at AECL's Chalk River Laboratories to remove tritium from moderately tritiated light water and to reclaim tritiated, downgraded heavy water. With only a few limitations, a single CECE (Combined Electrolysis and Catalytic Exchange) process configuration can be designed to remove tritium from heavy water or light water and upgrade heavy water. Such a design would have some restrictions on the nature of the feed-stock and tritium product, but could produce essentially tritium-free light or heavy water that is chemically pure. The extracted tritium is produced as a small quantity of tritiated heavy water. The overall plant capacity is fixed by the total amount of electrolysis and volume of catalyst. In this proposal, with 60 kA of electrolysis a throughput of 15 kg*h{sup -1} light water for detritiation, about 4 kg*h{sup -1} of heavy water for detritiation and about 27 kg*h{sup -1} of 98% heavy water for upgrading can be processed. Such a plant requires about 1,000 liters of AECL isotope exchange catalyst. The general design features and details of this multi-purpose CECE process are described in this paper, based on some practical choices of design criteria. In addition, we outline the small differences that must be accommodated and some compromises that must be made to make the plant capable of such flexible operation. (authors)

  5. Jarosite-water oxygen and hydrogen isotope fractionations: preliminary experimental data

    USGS Publications Warehouse

    Rye, R.O.; Stoffregen, R.E.

    1995-01-01

    Stable isotope studies of alunite have added a powerful tool for understanding geochemical processes in the surficial environment. Jarosite [KFe3(SO4)2(OH)6], like alunite, is a common mineral in the weathered portions of many sulfide-bearing ore deposits and mine drainages where its formation reflects acidic conditions produced by the oxidation of sulfides. This paper describes oxygen and hydrogen isotope fractionations in jarosite-water experiments over a temperature range of 100?? to 250??C and the extrapolation of the results to surface conditions. It also includes some general observations on the exchange reaction mechanism that are important for evaluating how well natural samples of jarosite retain primary isotopic compositions. -from Authors

  6. Extreme changes in stable hydrogen isotopes and precipitation characteristics in a landfalling Pacific storm

    USGS Publications Warehouse

    Coplen, T.B.; Neiman, P.J.; White, A.B.; Landwehr, J.M.; Ralph, F.M.; Dettinger, M.D.

    2008-01-01

    With a new automated precipitation collector we measured a remarkable decrease of 51??? in the hydrogen isotope ratio (?? 2H) of precipitation over a 60-minute period during the landfall of an extratropical cyclone along the California coast on 21 March 2005. The rapid drop in ??2H occurred as precipitation generation transitioned from a shallow to a much deeper cloud layer, in accord with synoptic-scale ascent and deep "seeder-feeder" precipitation. Such unexpected ?? 2H variations can substantially impact widely used isotope-hydrograph methods. From extreme ??2H values of -26 and -78???, we calculate precipitation temperatures of 9.7 and -4.2??C using an adiabatic condensation isotope model, in good agreement with temperatures estimated from surface observations and radar data. This model indicates that 60 percent of the moisture was precipitated during ascent as temperature decreased from 15??C at the ocean surface to -4??C above the measurement site.

  7. On-line technique for measuring stable oxygen and hydrogen isotopes from microliter quantities of water

    NASA Technical Reports Server (NTRS)

    Socki, R. A.; Romanek, C. S.; Gibson, E. K. Jr; Gibson EK, J. r. (Principal Investigator)

    1999-01-01

    Detailed here is a method for extracting and analyzing oxygen and hydrogen isotopes from 10 microL-sized water samples. Based on the traditional CO2-H2O equilibration technique, the oxygen isotope exchange reaction is done exclusively in sealed 6-mm (o.d.) Pyrex tubes at 25 degrees C, with full isotope exchange completed in at least 28 h. Using the same water sample employed in the 18O equilibration, D/H extractions are done in separate sealed 6-mm (o.d.) Pyrex tubes by reaction with Zn at 450 degrees C to form H2(g). Provided that a correction factor is applied to 18O analyses, accuracy and precision for both 18O and D/H are comparable to standard techniques using much larger samples.

  8. Preliminary Hydrogen Isotope Data from Volcanic Glass in the Peruvian Andes

    NASA Astrophysics Data System (ADS)

    White, E.; Cassel, E. J.

    2016-12-01

    The Central Andes contain the highest ocean-continent subduction-driven plateau in the world, and are a model for the complex interactions between climate and topography. Existing tectonic models for Andean orogenesis vary widely in both the timing and driving mechanisms of surface uplift. Proposed mechanisms include early Cenozoic uplift in the west during contractional deformation, gradual late Cenozoic surface uplift resulting from continuous crustal thickening and shortening, and rapid late Cenozoic surface uplift from delamination of the South American lithosphere. To constrain the orogenic and climate history of southern Peru, we are using hydrogen isotope data from volcanic glasses sampled from Eocene-Pleistocene vitric ignimbrites deposited from the Pacific coast across the Western Cordillera magmatic arc and northern Altiplano. Ignimbrites are partially welded to unwelded, range in thickness from 10-65m, and are composed of 5-35% phenocrysts of biotite, quartz, and feldspar, with up to 40% lithic and pumice clasts. Many ignimbrites consist of multiple flow units and interbedded fluvial sediments and are commonly underlain or capped by andesitic, basaltic, and dacitic flows. Initial hydrogen isotope values from ancient meteoric water preserved in volcanic glasses (δDglass) from 40-2 Ma show decreasing δD values for samples located in the high Western Cordillera, while samples closer to the Pacific coast show little variation in δD over the past 40 Ma. Further sampling over a greater geographic range, coupled with new high precision geochronology and modeling of the influence of topography and climate on isotope distillation rates, is needed to determine the most likely drivers for changes in δD values and to quantify the magnitude of those changes. δDglass values will be compared with multiple topographic scenarios using a three-dimensional isotope-tracking global climate model, calibrated with modern hydrogen isotope values from soil, precipitation

  9. Hydrogen adsorption in a highly stable porous rare-earth metal-organic framework: sorption properties and neutron diffraction studies.

    PubMed

    Luo, Junhua; Xu, Hongwu; Liu, Yun; Zhao, Yusheng; Daemen, Luke L; Brown, Craig; Timofeeva, Tatiana V; Ma, Shengqian; Zhou, Hong-Cai

    2008-07-30

    A highly stable porous lanthanide metal-organic framework, Y(BTC)(H2O).4.3H2O (BTC = 1,3,5-benzenetricarboxylate), with pore size of 5.8 A has been constructed and investigated for hydrogen storage. Gas sorption measurements show that this porous MOF exhibits highly selective sorption behaviors of hydrogen over nitrogen gas molecules and can take up hydrogen of about 2.1 wt % at 77 K and 10 bar. Difference Fourier analysis of neutron powder diffraction data revealed four distinct D2 sites that are progressively filled within the nanoporous framework. Interestingly, the strongest adsorption sites identified are associated with the aromatic organic linkers rather than the open metal sites, as occurred in previously reported MOFs. Our results provide for the first time direct structural evidence demonstrating that optimal pore size (around 6 A, twice the kinetic diameter of hydrogen) strengthens the interactions between H2 molecules and pore walls and increases the heat of adsorption, which thus allows for enhancing hydrogen adsorption from the interaction between hydrogen molecules with the pore walls rather than with the normally stronger adsorption sites (the open metal sites) within the framework. At high concentration H2 loadings (5.5 H2 molecules (3.7 wt %) per Y(BTC) formula), H2 molecules form highly symmetric novel nanoclusters with relatively short H2-H2 distances compared to solid H2. These observations are important and hold the key to optimizing this new class of rare metal-organic framework (RMOF) materials for practical hydrogen storage applications.

  10. Reversible hydrogen adsorption on Co/N4 cluster embedded in graphene: The role of charge manipulation

    NASA Astrophysics Data System (ADS)

    Omidvar, Akbar

    2017-08-01

    Electrical charging of Co/N4 cluster embedded in graphene (Co/N4/G) is proposed as an approach for electrocatalytically switchable hydrogen adsorption. Using density functional theory, we found that the H2 molecule is weakly adsorbed on the uncharged Co/N4/G cluster. Our results show that the adsorption energy of hydrogen molecule on Co/N4/G cluster is significantly increased by introducing extra positive charges into the cluster. Once the charges are removed, H2 molecule spontaneously desorb from the Co/N4/G absorbent. Therefore, this approach promises both facile reversibility and tunable kinetics without the need of specific catalysts. Our study indicates that the Co/N4/G nanomaterial is excellent absorbent for controllable and reversible adsorption and release of H2.

  11. Hydrogen production from food wastes and gas post-treatment by CO2 adsorption.

    PubMed

    Redondas, V; Gómez, X; García, S; Pevida, C; Rubiera, F; Morán, A; Pis, J J

    2012-01-01

    The production of H(2) by biological means, although still far from being a commercially viable proposition, offers great promise for the future. Purification of the biogas obtained may lead to the production of highly concentrated H(2) streams appropriate for industrial application. This research work evaluates the dark fermentation of food wastes and assesses the possibility of adsorbing CO(2) from the gas stream by means of a low cost biomass-based adsorbent. The reactor used was a completely stirred tank reactor run at different hydraulic retention times (HRTs) while the concentration of solids of the feeding stream was kept constant. The results obtained demonstrate that the H(2) yields from the fermentation of food wastes were affected by modifications in the hydraulic retention time (HRT) due to incomplete hydrolysis. The decrease in the duration of fermentation had a negative effect on the conversion of the substrate into soluble products. This resulted in a lower amount of soluble substrate being available for metabolisation by H(2) producing microflora leading to a reduction in specific H(2) production. Adsorption of CO(2) from a gas stream generated from the dark fermentation process was successfully carried out. The data obtained demonstrate that the column filled with biomass-derived activated carbon resulted in a high degree of hydrogen purification. Co-adsorption of H(2)S onto the activated carbon also took place, there being no evidence of H(2)S present in the bio-H(2) exiting the column. Nevertheless, the concentration of H(2)S was very low, and this co-adsorption did not affect the CO(2) capture capacity of the activated carbon.

  12. Adsorption of hydrogen sulphide from aqueous solutions using modified nano/micro fibrillated cellulose.

    PubMed

    Hokkanen, Sanna; Repo, Eveliina; Bhatnagar, Amit; Tang, Walter Zhonghong; Sillanpää, Mika

    2014-01-01

    In the present study, microfibrillated cellulose (MFC) was modified by aminopropyltriethoxysilane (APS), hydroxy-carbonated apatite (HAP), or epoxy in order to produce novel nanostructured adsorbents for the removal of hydrogen sulphide (H2S) from the aqueous solutions. Structural properties of the modified MFC materials were examined using a scanning electron microscope, Fourier transform infrared spectroscopy and acid/base titration. These methods were used to verify the presence of nanostructures on the adsorbents surfaces as well as functionalities suitable for H2S adsorption. Adsorption of H2S by prepared adsorbents was investigated in batch mode under different experimental conditions, i.e., varying pH and H2S concentrations. H2S uptake was found to be 103.95, 13.38 and 12.73 mg/g by APS/MFC, HAP/MFC and epoxy/MFC, respectively from 80 mg/L H2S solution. The equilibrium data were best described by the Langmuir isotherm for HAP/MFC and APS/MFC and the Sips isotherm for epoxy/MFC.

  13. Hydrogen adsorption at the graphene surface: A vdW-DF perspective

    SciTech Connect

    Cooper, Valentino R; Ihm, Yungok; Morris, James R

    2012-01-01

    We use the recently developed van der Waals density functional (vdW-DF) along with the C09x exchange functional to explore the interactions of molecular hydrogen with a single sheet of graphene. Our calculations demonstrate the importance of the inclusion of dispersion interactions for evaluating the adsorption capacity of graphitic, sparsely packed materials. In particular we show that, although the commonly used local density approximation (LDA) exchange-correlation functional gives reasonable H$_2$-graphene separation distances, these interactions are in fact too strong and decrease too rapidly as the H$_2$-graphene distance increases. On the other hand, calculations employing the generalized gradient approximation (GGA) for exchange and correlation exhibit very little binding. The vdW-DF$^{\\rm C09x}$ functional, however, gives binding very similar to benchmark second-order M$\\o$ller-Plesset (MP2) theory results for the H$_2$-coronene interaction and has an appropriate long range interaction with the graphene sheet. This shortcoming of the LDA and GGA functionals is shown to have significant consequences on the overall adsorption densities of H$_2$ near the graphene, thus emphasizing the fundamental importance of properly characterizing the interactions of adsorbed molecules in porous media.

  14. Hydrogen-isotope fractionation in aluminum hydroxides: Synthesis products versus natural samples from bauxites

    NASA Astrophysics Data System (ADS)

    Vitali, Frédéric; Longstaffe, Fred J.; Bird, Michael I.; Gage, Karie Lyne; Caldwell, W. Glen E.

    2001-05-01

    - Hydrogen-isotope data have been gathered for synthetic aluminum hydroxides precipitated over 3 to 121 months at temperatures varying between 8 and 51°C. All three Al(OH) 3 polymorphs, gibbsite, nordstrandite, and bayerite, were generated during the synthesis, but gibbsite was dominant in most samples and commonly the only phase present. At <10°C, hydrogen-isotope equilibrium between the synthetic Al-hydroxides and water was not achieved until more than 2 years had elapsed. Using pure gibbsite samples, an average α gibbsite-waterH value of 0.998 ± 0.006 was obtained between 9 and 51°C after 10 years of synthesis. Based on these results plus data for naturally occurring gibbsite from bauxite deposits, an α gibbsite-waterH value of 0.995 ± 0.003 was obtained for surficial temperatures. Using this value and oxygen-isotope results, the following "gibbsite line" is proposed for its formation from meteoric water at 20°C: δD = 7.84 δ 18O - 114.2. Most naturally occurring gibbsite samples plot about this line, which indicates their direct precipitation from solution. However, a few samples of gibbsite, especially those from Hawaii, plot to the right of the "gibbsite line" and likely inherited part of their isotopic composition from precursor kaolinite.

  15. Hydrogen Isotope Fractionation in Aquatic Primary Producers: Implications for Food Web Studies

    NASA Astrophysics Data System (ADS)

    Hondula, K. L.; Pace, M. L.; Cole, J. J.; Batt, R. D.

    2011-12-01

    Hydrogen in the organic matter of aquatic plants has a lower relative abundance of the deuterium isotope in comparison to hydrogen in the surrounding water due to a series of fractionation processes including photosynthesis and the biosynthesis of lipids. Expected differences between the deuterium values of different types of plant tissue have been used to observe terrestrial contributions to aquatic food webs and to discriminate organic matter sources in 3-isotope studies with more precision than in 2-isotope studies, however some values used in these studies are derived from an estimated fractionation value (ɛ) between water and plant tissue. We found significant differences in fractionation values between different groups of aquatic plants sampled from three system types: lakes, river, and coastal lagoon. Fractionation values between water and plant tissue of macrophytes and marine macroalgae were more similar to those of terrestrial plants and distinctly different than those of benthic microalgae and phytoplankton. Incorporating the variability in fractionation values between plant types will improve models and experimental designs used in isotopic food web studies for aquatic systems.

  16. Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments, Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Estep, Marilyn L. F.

    1984-03-01

    Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO 2 concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in 12C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ 13C of organic carbon was ˜ -12%., whereas at 900 ppm total inorganic C, the δ 13C of similar species was ˜ -25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ 13C values were ˜ -18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ 13C values (to -30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ 13C of the original organic matter. The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to -74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO 2 levels, pH, temperature, and species composition between modern stromatolites and their environment and those of

  17. A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

    NASA Astrophysics Data System (ADS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Flemming, Roberta L.; Rossman, George R.; Eiler, John M.; Neal, Clive R.; Osinski, Gordon R.

    2017-09-01

    Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth-Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from -280 to + 310 ‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about - 280 ‰, evolving to about + 310 ‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

  18. Investigations of intramolecular hydrogen bonding in three types of Schiff bases by 2H and 3H NMR isotope effects.

    PubMed

    Schilf, Wojciech; Bloxsidge, James P; Jones, John R; Lu, Shui-Yu

    2004-06-01

    Hydrogen bonding within the structures of three Schiff bases (1-3), obtained by condensation of 4-methoxy-, 5-methoxy- and 4,6-dimethoxysalicylaldehyde with methylamine, was investigated by measuring deuterium and tritium NMR isotope effects. The primary deuterium and tritium isotope effects (delta(XH)-delta(XD/T)) and secondary one-bond nitrogen deuterium effect appear to be very useful parameters for defining the character of intramolecular hydrogen bonds. The tritium isotope effects were also determined for nitrogen-hydrogen one-bond coupling constants for both 4-methoxy and 4,6-dimethoxy derivatives. These parameters are seen to be highly sensitive to hydrogen bond characteristics and can be used to distinguish localized and tautomeric hydrogen bonds.

  19. Investigation related to hydrogen isotopes separation by cryogenic distillation

    SciTech Connect

    Bornea, A.; Zamfirache, M.; Stefanescu, I.; Preda, A.; Balteanu, O.; Stefan, I.

    2008-07-15

    Research conducted in the last fifty years has shown that one of the most efficient techniques of removing tritium from the heavy water used as moderator and coolant in CANDU reactors (as that operated at Cernavoda (Romania)) is hydrogen cryogenic distillation. Designing and implementing the concept of cryogenic distillation columns require experiments to be conducted as well as computer simulations. Particularly, computer simulations are of great importance when designing and evaluating the performances of a column or a series of columns. Experimental data collected from laboratory work will be used as input for computer simulations run at larger scale (for The Pilot Plant for Tritium and Deuterium Separation) in order to increase the confidence in the simulated results. Studies carried out were focused on the following: - Quantitative analyses of important parameters such as the number of theoretical plates, inlet area, reflux flow, flow-rates extraction, working pressure, etc. - Columns connected in series in such a way to fulfil the separation requirements. Experiments were carried out on a laboratory-scale installation to investigate the performance of contact elements with continuous packing. The packing was manufactured in our institute. (authors)

  20. Hydrogen isotopic composition of individual n-alkanes as an intrinsic tracer for bioremediation and source identification of petroleum contamination.

    PubMed

    Pond, Kristy L; Huang, Yongsong; Wang, Yi; Kulpa, Charles F

    2002-02-15

    The isotopic signatures of crude oil hydrocarbons are potentially powerful intrinsic tracers to their origins and the processes by which the oils are modified in the environment. Stable carbon isotopic data are of limited use for studying petroleum contaminants because of the relatively small amount of isotopic fractionation that occurs during natural processes. Hydrogen isotopes, in contrast, are commonly fractionated to a much greater extent and as a result display larger variations in delta values. We studied the effect of in vitro aerobic biodegradation on the hydrogen isotopic composition of individual n-alkanes from crude oil. The isotopic analysis was conducted using gas chromatography-thermal conversion-isotope ratio mass spectrometry. In general, biodegradation rates decreased with increasing hydrocarbon chain length, consistent with previous studies. More importantly the n-alkanes that were degraded at the fastest rates (n-C15 to n-C18) also showed the largest overall isotopic fractionation (approximately 12-25 per thousand deuterium enrichment), suggesting that the lower molecular weight n-alkanes can be used to monitor in-situ bioremediation of crude oil contamination. The hydrogen isotopic compositions of the longer chain alkanes (n-C19 to n-C27) were relatively stable during biodegradation (<5%o overall deuterium enrichment), indicating that these compounds are effective tracers for oil-source identification studies.

  1. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

    2012-04-01

    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  2. Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall, Tissint

    NASA Astrophysics Data System (ADS)

    Mane, P.; Hervig, R.; Wadhwa, M.; Garvie, L. A. J.; Balta, J. B.; McSween, H. Y.

    2016-11-01

    The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth-based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of -250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine-hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial-like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock-related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is -116 ± 94‰, which is the lowest value measured in a phase in the

  3. Absorption/desorption of hydrogen isotopes and isotopic waters by Zr-alloy getters

    SciTech Connect

    Ichimura, K.; Matsuyama, M.; Watanabe, K.; Takeuchi, T.

    1988-07-01

    Zr-alloy getters have been applied to tritium handling and vacuum conditioning for fusion devices. Some of their properties, however, should be improved to apply them in future devices. From this viewpoint, we have studied the effects of alloying on the getter properties of Zr alloys. We found that the activation energy of absorption and desorption of hydrogen varied considerably with alloying. The activation energy for hydrogen absorption was 0.74 for Zr/sub 61/Al/sub 39/, 0.01 for Zr/sub 57/V/sub 36/Fe/sub 7/, 0.63 for Zr/sub 67/Ni/sub 33/, and 2.8 kcal/mol for Zr/sub 85/Ni/sub 15/, whereas that for Zr was 2.6 kcal/mol. The heat of hydrogen absorption was 27.8 kcal/mol for Zr: it changed with alloying as 32.0--33.4 (Zr/sub 61/Al/sub 39/), 27.8--28.4 (Zr/sub 57/V/sub 36/Fe/sub 7/), 29.0 (Zr/sub 67/Ni/sub 33/), and 28.0 (Zr/sub 85/Ni/sub 15/). In addition, the ratio of the pumping speed of water vapor to that of hydrogen at room temperature varied with alloying element: for example, 1/40 for Zr/sub 57/V/sub 36/Fe/sub 7/ and 1/4 for Zr/sub 67/Ni/sub 33/. The alloying effects mentioned above are considered due to modification of the electronic and/or geometric structure of Zr with alloying.

  4. Trends in the adsorption and reactivity of hydrogen on magnesium silicate nanoclusters.

    PubMed

    Oueslati, Ichraf; Kerkeni, Boutheïna; Bromley, Stefan T

    2015-04-14

    We study nanoclusters of Mg-rich olivine and pyroxene (having (MgO)6(SiO2)3 and (MgO)4(SiO2)4 compositions) with respect to their reactivity towards hydrogen atoms, using density functional calculations. Ultrasmall silicate particles are fundamental intermediates in cosmic dust grain formation and processing, and are thought to make up a significant mass fraction of the grain population. Due to their nanoscale dimensions and high surface area to bulk ratios, they are likely to also have a disproportionately large influence on surface chemistry in the interstellar medium. This work investigates the potential role of silicate nanoclusters in vital interstellar hydrogen-based chemistry by studying atomic H adsorption and H2 formation. Our extensive set of calculations confirm the generality of a Brønsted-Evans-Polanyi (BEP) relation between the H2 reaction barrier and the 2Hchem binding energy, suggesting it to be independent of silicate dust grain shape, size, crystallinity and composition. Our results also suggest that amorphous/porous grains with forsteritic composition would tend to dissociate H2, but relatively Mg-poor silicate grains (e.g. enstatite composition) and/or more crystalline/compact silicate grains would tend to catalyse H2 formation. The high structural thermostability of silicate nanoclusters with respect to the heat released during exothermic H2 formation reactions is also verified.

  5. Adsorption isotherms for hydrogen chloride (HCl) on ice surfaces between 190 and 220 K.

    PubMed

    Zimmermann, S; Kippenberger, M; Schuster, G; Crowley, J N

    2016-05-18

    The interaction of hydrogen chloride (HCl) with ice surfaces at temperatures between 190 and 220 K was investigated using a coated-wall flow-tube connected to a chemical ionization mass spectrometer. Equilibrium surface coverages of HCl were determined at gas phase concentrations as low as 2 × 10(9) molecules cm(-3) (∼4 × 10(-8) Torr at 200 K) to derive Langmuir adsorption isotherms. The data are described by a temperature independent partition coefficient: KLang = (3.7 ± 0.2) × 10(-11) cm(3) molecule(-1) with a saturation surface coverage Nmax = (2.0 ± 0.2) × 10(14) molecules cm(-2). The lack of a systematic dependence of KLang on temperature contrasts the behaviour of numerous trace gases which adsorb onto ice via hydrogen bonding and is most likely related to the ionization of HCl at the surface. The results are compared to previous laboratory studies, and the equilibrium partitioning of HCl to ice surfaces under conditions relevant to the atmosphere is evaluated.

  6. Fractionation of sulfur and hydrogen isotopes in Desulfovibrio vulgaris with perturbed DsrC expression.

    PubMed

    Leavitt, William D; Venceslau, Sofia S; Pereira, Inês A C; Johnston, David T; Bradley, Alexander S

    2016-10-01

    Dissimilatory sulfate reduction is the central microbial metabolism in global sulfur cycling. Understanding the importance of sulfate reduction to Earth's biogeochemical S cycle requires aggregating single-cell processes with geochemical signals. For sulfate reduction, these signals include the ratio of stable sulfur isotopes preserved in minerals, as well as the hydrogen isotope ratios and structures of microbial membrane lipids preserved in organic matter. In this study, we cultivated the model sulfate reducer, Desulfovibrio vulgaris DSM 644(T), to investigate how these parameters were perturbed by changes in expression of the protein DsrC. DsrC is critical to the final metabolic step in sulfate reduction to sulfide. S and H isotopic fractionation imposed by the wild type was compared to three mutants. Discrimination against (34)S in sulfate, as calculated from the residual reactant, did not discernibly differ among all strains. However, a closed-system sulfur isotope distillation model, based on accumulated sulfide, produced inconsistent results in one mutant strain IPFG09. Lipids produced by IPFG09 were also slightly enriched in (2)H. These results suggest that DsrC alone does not have a major impact on sulfate-S, though may influence sulfide-S and lipid-H isotopic compositions. While intriguing, a mechanistic explanation requires further study under continuous culture conditions.

  7. Hydrogen production from food wastes and gas post-treatment by CO{sub 2} adsorption

    SciTech Connect

    Redondas, V.; Gomez, X.; Garcia, S.; Pevida, C.; Rubiera, F.; Moran, A.; Pis, J.J.

    2012-01-15

    Highlights: Black-Right-Pointing-Pointer The dark fermentation process of food wastes was studied over an extended period. Black-Right-Pointing-Pointer Decreasing the HRT of the process negatively affected the specific gas production. Black-Right-Pointing-Pointer Adsorption of CO{sub 2} was successfully attained using a biomass type activated carbon. Black-Right-Pointing-Pointer H{sub 2} concentration in the range of 85-95% was obtained for the treated gas-stream. - Abstract: The production of H{sub 2} by biological means, although still far from being a commercially viable proposition, offers great promise for the future. Purification of the biogas obtained may lead to the production of highly concentrated H{sub 2} streams appropriate for industrial application. This research work evaluates the dark fermentation of food wastes and assesses the possibility of adsorbing CO{sub 2} from the gas stream by means of a low cost biomass-based adsorbent. The reactor used was a completely stirred tank reactor run at different hydraulic retention times (HRTs) while the concentration of solids of the feeding stream was kept constant. The results obtained demonstrate that the H{sub 2} yields from the fermentation of food wastes were affected by modifications in the hydraulic retention time (HRT) due to incomplete hydrolysis. The decrease in the duration of fermentation had a negative effect on the conversion of the substrate into soluble products. This resulted in a lower amount of soluble substrate being available for metabolisation by H{sub 2} producing microflora leading to a reduction in specific H{sub 2} production. Adsorption of CO{sub 2} from a gas stream generated from the dark fermentation process was successfully carried out. The data obtained demonstrate that the column filled with biomass-derived activated carbon resulted in a high degree of hydrogen purification. Co-adsorption of H{sub 2}S onto the activated carbon also took place, there being no evidence of H

  8. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

    1996-01-01

    Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are

  9. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

    1996-01-01

    Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are

  10. Hydrogen isotope exchange and conditioning in graphite limiters used in TFTR

    SciTech Connect

    LaMarche, P.H.; Dylla, H.F.; McCarthy, P.J.; Ulrickson, M.

    1986-02-01

    Isotopic exchange experiments performed in TFTR are used to examine the outgassing and diffusive properties of graphite used as the plasma limiter. Changeover from hydrogen to deuterium for different periods ranges from approx.600 to 60 plasma discharges, which appears to be correlated to the limiter temperature. We present a simple analytical model that predicts a fast transient (approx.10 plasma discharges) changeover where the deuterium fueling dilutes the adsorbed and near-surface hydrogen, and a slowly changing term where bulk hydrogen diffuses to the surface. Using this model we can extract an activation energy for diffusion of 0.15 +- 0.02 eV. We hypothesize that interpore diffusion for this porous (approx.15%) material is consistent with our observations. 19 refs.

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

    PubMed

    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.

  12. Hydrogen Cylinder Storage Array Explosion Evaluations at the High Flux Isotope Reactor

    SciTech Connect

    Cook, David Howard; Griffin, Frederick P; Hyman III, Clifton R

    2010-01-01

    The safety analysis for a recently-installed cold neutron source at the High Flux Isotope Reactor (HFIR) involved evaluation of potential explosion consequences from accidental hydrogen jet releases that could occur from an array of hydrogen cylinders. The scope of the safety analysis involved determination of the release rate of hydrogen, the total quantity of hydrogen assumed to be involved in the explosion, the location of an ignition point or center of the explosion from receptors of interest, and the peak overpressure at the receptors. To evaluate the total quantity of hydrogen involved in the explosion, a 2D model was constructed of the jet concentration and a radial-axial integral over the jet cloud from the centerline to the flammability limit of 4% was used to determine the hydrogen mass to be used as a source term. The location of the point source was chosen as the peak of the jet centerline concentration profile. Consequences were assessed using a combination of three methods for estimating local overpressure as a function of explosion source strength and distance: the Baker-Strehlow method, the TNT-equivalence method, and the TNO method. Results from the explosions were assessed using damage estimates in screening tables for buildings and industrial equipment.

  13. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Reeves, Eoghan P.; Seewald, Jeffrey S.; Sylva, Sean P.

    2012-01-01

    To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1-C5n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323 °C and 35-36 MPa. Extensive and reversible incorporation of water-derived hydrogen into C2-C5n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3-C5n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkanes and their corresponding alkenes facilitates rapid 2H/1H exchange between water and alkyl-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.

  14. Suppression of hydrogenated carbon film deposition and hydrogen isotope retention by nitrogen addition into cold remote H/D and CH4 mixture plasmas

    NASA Astrophysics Data System (ADS)

    Iida, K.; Notani, M.; Uesugi, Y.; Tanaka, Y.; Ishijima, T.

    2015-08-01

    Control of tritium retention and its removal from the first wall of future fusion devices are one of the most crucial issues for safety and effective use for fuel. Nitrogen addition into remote edge plasmas has been considered and tested as an effective method for suppression of carbon film deposition and reduction of hydrogen isotope absorption in the deposited films. In this paper we have investigated the scavenger effects of nitrogen injected into low temperature D2/CH4 plasmas on hydrogenated carbon film growth using a small helical device. The result of the deposition shows that the key reactive particles with CN and ND(H) bonds to suppression of hydrogenated carbon film growth and hydrogen isotope absorption are much slowly generated compared with hydrocarbon particles such as CD(H)x and C2D(H)x. This may be due to the slow atomic nitrogen diffusion into hydrogenated carbon layer and the chemical equilibrium between nitrogen absorption.

  15. Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

    NASA Technical Reports Server (NTRS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Rossman, George R.; Eiler, John M.; Neal, Clive R.

    2015-01-01

    The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands.

  16. Experimental Investigation of Irradiation-driven Hydrogen Isotope Fractionation in Analogs of Protoplanetary Hydrous Silicate Dust

    NASA Astrophysics Data System (ADS)

    Roskosz, Mathieu; Laurent, Boris; Leroux, Hugues; Remusat, Laurent

    2016-11-01

    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.

  17. Dye-adsorption capacity of high surface-area hydrogen titanate nanosheets processed via modified hydrothermal method.

    PubMed

    Padinhattayil, Hareesh; Augustine, Rimesh; Shukla, Satyajit

    2013-04-01

    High surface-area (380 m2 x g(-1)) hydrogen titanate nanosheets (HTNS) processed via the modified hydrothermal method have been utilized for the removal of methylene blue (MB) dye from an aqueous solution via the surface-adsorption process involving the electrostatic attraction mechanism. The HTNS have been characterized using the transmission electron microscope (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) specific surface-area measurement techniques. The amount of MB dye adsorbed on the surface of HTNS at equilibrium (q(e)) has been examined as a function of contact time, initial dye-concentration, and initial solution-pH. Within the investigated range of initial solution-pH (2.5-11), the MB dye adsorption on the surface of HTNS has been observed to follow the pseudo-second-order kinetics with the dye-adsorption capacity of 119 mg x g(-1) at the initial solution-pH of - 10. The adsorption equilibrium follows the Langmuir isotherm within the initial solution-pH range of 2.5-10. However, in a highly basic solution (initial solution-pH -11), the adsorption equilibrium has been observed to follow the Langmuir, Freundlich, and Dubinin-Kaganer-Radushkevich (DKR) models in the different ranges of initial MB dye concentration. The mere dependence on the DKR model has not been observed within the investigated range of initial solution-pH. The differences in the dye-adsorption characteristics and capacity of HTNS, compared with those of hydrogen titanate nanotubes, have been attributed to the difference in their specific surface-area. Irrespective of the morphology, the maximum coverage of MB dye on the surface of hydrogen titanate has been noted to be the same (52%).

  18. The Use of Stable Hydrogen Isotopes as a Geothermometer in Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Proskurowski, G.; Lilley, M. D.; Früh-Green, G. L.; Olson, E. J.; Kelley, D. S.

    2004-12-01

    Terrestrial geothermal work by Arnason in the 1970's demonstrated the utility of stable hydrogen isotopes as a geothermometer[1]. However, with the exception of two data points from 9°N in a study by Horibe and Craig[2], the value of this geothermometer in hydrothermal systems has never been rigorously assessed. Equilibrium fractionation factors for H2-H2O and H2-CH4 have previously been determined experimentally and theoretically over a range of temperatures and provide an expression relating alpha (fractionation) and temperature. We have measured the dD of H2(g), CH4(g) and H2O from a diverse selection of hydrothermal vent localities including Lost City, Middle Valley, Endeavour, Guaymas, Logatchev, Broken Spur, and SWIR. These samples were chosen to represent a wide range of fluid temperatures and a variety of environmental settings. We see a strong correlation between measured vent temperature and predicted vent temperature using both the hydrogen-water and the methane-hydrogen geothermometers over a temperature range of 25-400°C. In the case of the H2-H2O geothermometer, the predicted temperatures are slightly elevated with respect to the measured temperatures at the low temperature Lost City site, and are in good agreement at high temperature vent sites. The H2-CH4 geothermometer predicts temperatures that are 40-80°C elevated with respect to the measured temperature in both the low and high temperature sites. These measurements demonstrate that the hydrogen isotope geothermometer in the hydrogen-methane-water system is robust in hydrothermal systems and may be a useful tool in determining the temperature of the root zone. 1. Arnason, B., The Hydrogen-Water Isotope Thermometer Applied to Geothermal Areas In Iceland. Geothermics, 1977. 5: p. 75-80. 2. Horibe, Y. and H. Craig, D/ H fractionation in the system methane-hydrogen-water. Geochimica et Cosmochimica Acta, 1995. 59(24): p. 5209-5217.

  19. Hydrogen adsorption strength and sites in the metal organic framework MOF5: Comparing experiment and model calculations

    NASA Astrophysics Data System (ADS)

    Mulder, F. M.; Dingemans, T. J.; Schimmel, H. G.; Ramirez-Cuesta, A. J.; Kearley, G. J.

    2008-07-01

    Hydrogen adsorption in porous, high surface area, and stable metal organic frameworks (MOF's) appears a novel route towards hydrogen storage materials [N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, O.M. Yaghi, Science 300 (2003) 1127; J.L.C. Rowsell, A.R. Millward, K. Sung Park, O.M. Yaghi, J. Am. Chem. Soc. 126 (2004) 5666; G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guegan, Chem. Commun. (2003) 2976; T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Férey, Chem. Eur. J. 10 (2004) 1373]. A prerequisite for such materials is sufficient adsorption interaction strength for hydrogen adsorbed on the adsorption sites of the material because this facilitates successful operation under moderate temperature and pressure conditions. Here we report detailed information on the geometry of the hydrogen adsorption sites, based on the analysis of inelastic neutron spectroscopy (INS). The adsorption energies for the metal organic framework MOF5 equal about 800 K for part of the different sites, which is significantly higher than for nanoporous carbon materials (˜550 K) [H.G. Schimmel, G.J. Kearley, M.G. Nijkamp, C.T. Visser, K.P. de Jong, F.M. Mulder, Chem. Eur. J. 9 (2003) 4764], and is in agreement with what is found in first principles calculations [T. Sagara, J. Klassen, E. Ganz, J. Chem. Phys. 121 (2004) 12543; F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113]. Assignments of the INS spectra is realized using comparison with independently published model calculations [F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113] and structural data [T. Yildirim, M.R. Hartman, Phys. Rev. Lett. 95 (2005) 215504].

  20. Effect of O2 pressure on the hydrothermal growth of CuO hierarchical microstructures: characterization and hydrogen adsorption capacity

    NASA Astrophysics Data System (ADS)

    Roble, M.; Diaz-Droguett, D.

    2017-08-01

    In the present study, the effect of injected O2 pressure to a hydrothermal reactor on the growth, morphology, structure and hydrogen adsorption properties of CuO hierarchical microstructures was investigated. The synthesis consisted of a simple one-step hydrothermal reaction using copper chloride and aqueous ammonia. Hydrothermal reactions were carried at 200 °C at reaction times of 1 and 12 h injecting at the beginning of the synthesis O2 pressures of 0, 30 or 60 bar. The samples were characterized by SEM and EDS for morphological and chemical information, XRD for determination of crystalline phases, lattice parameters and crystallinity grade using Rietveld refinement. Specific surface area was determined using BET method from nitrogen adsorption/desorption isotherm measurements. Hydrogen adsorption capacities at 20 °C were studied for key samples using the quartz crystal microbalance technique under gas exposure pressures between 3 and 100 Torr. It was found that the samples were of monoclinic CuO phase consisting mainly of sphere-like hierarchical microstructures of different average sizes assembled by sheets. The effect of the reactor pressure was mainly seen on average size of the CuO microstructures due to changes in the growth rate, specifically during the first stages of the hydrothermal reaction. Reactor pressure induced changes on the crystallinity of the samples were determined but no correlation was stated. Hydrogen adsorption capacities of studied samples measured at 100 Torr ranged from 0.27 to 0.6 wt%, indicating a good performance as compared with other reported values. Oxygen deficiency in CuO can influence on the hydrogen adsorption capacity.

  1. An instrumental and numerical method to determine the hydrogenic ratio in isotopic experiments in the TJ-II stellarator

    SciTech Connect

    Baciero, A. Zurro, B.; Martínez, M.

    2014-11-15

    The isotope effect is an important topic that is relevant for future D-T fusion reactors, where the use of deuterium, rather than hydrogen, may lean to improved plasma confinement. An evaluation of the ratio of hydrogen/deuterium is needed for isotope effect studies in current isotopic experiments. Here, the spectral range around H{sub α} and D{sub α} lines, obtained with an intensified multi-channel detector mounted to a 1-m focal length spectrometer, is analyzed using a fit function that includes several Gaussian components. The isotopic ratio evolution for a single operational day of the TJ-II stellarator is presented. The role of injected hydrogen by Neutral Beam Injection heating is also studied.

  2. Evaluating the role of re-adsorption of dissolved Hg(2+) during cinnabar dissolution using isotope tracer technique.

    PubMed

    Jiang, Ping; Li, Yanbin; Liu, Guangliang; Yang, Guidi; Lagos, Leonel; Yin, Yongguang; Gu, Baohua; Jiang, Guibin; Cai, Yong

    2016-11-05

    Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbed Hg on cinnabar surface via the reduction in spiked (202)Hg(2+). By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred μgL(-1), while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. These results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies.

  3. Evaluating the role of re-adsorption of dissolved Hg2+ during cinnabar dissolution using isotope tracer technique

    DOE PAGES

    Jiang, Ping; Li, Yanbin; Liu, Guangliang; ...

    2016-06-02

    Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbedmore » Hg on cinnabar surface via the reduction in spiked 202Hg2+. By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred g L–1, while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. Lastly, these results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies.« less

  4. Dissociative Adsorption of Hydrogen and Oxygen on Palladium Clusters:  A Comparison with the (111) Infinite Surface.

    PubMed

    Roques, Jérôme; Lacaze-Dufaure, Corinne; Mijoule, Claude

    2007-05-01

    We report a density-functional study of some properties of the dissociative interaction of hydrogen and oxygen molecules on small palladium clusters (n = 5, 7, and 10). The calculated physisorption and chemisorption energies are compared with those of the infinite (111) palladium surface. First, adsorption of atomic hydrogen and oxygen is investigated on the Pd5, Pd7, and Pd10 clusters. Second, the interaction between H2 (O2) and the small Pd5 cluster is examined and compared to the process occurring on an infinite (111) surface. Finally, the simultaneous adsorption of two hydrogen (oxygen) atoms is analyzed in detail. As shown in a previous work, the binding energy of the first hydrogen (oxygen) atom does not depend significantly on the cluster size, and small two-layer clusters (n ≤ 10) can be used to determine with accuracy the interaction of atomic adsorbates with an infinite (111) palladium surface. In this study, we show that the dissociative chemisorption of H2 and more especially of O2 on a small palladium cluster may lead to erroneous binding energy:  the cluster's size may prevent an accurate description of the adsorbate-adsorbate interaction as a function of their distance. It is demonstrated that a good choice of both the size and the shape of the cluster is preponderant for a good description of the dissociative adsorption of H2 and O2 on an infinite (111) surface.

  5. Measurements of Hydrogen and Helium Isotopes with the BESS-Polar II Instrument

    NASA Astrophysics Data System (ADS)

    Picot-Clemente, Nicolas; BESS-Polar Collaboration

    2015-04-01

    The Balloon-Borne Experiment with a Superconducting Spectrometer (BESS-Polar II) flew successfully over Antarctica for 24.5 days in December 2007 through January 2008 during a period of minimum Solar activity. BESS-Polar II is configured with a solenoidal superconducting magnet and a suite of precision particle detectors. It can accurately identify hydrogen and helium isotopes among the incoming cosmic-ray nuclei with energies from 0.2 up to about 1.5 GeV/n. The long duration of the flight, and the good stability of the detectors increased the number of cosmic-ray events previously recorded with BESS-Polar I by a factor of 5, reaching about 4.7 billion collected particles. This allows to study and measure energy spectrum of hydrogen and helium isotope fluxes with unprecedented precision. The isotope flux and ratio measurements with BESS-Polar II will be presented and compared to previous measurements and theoretical predictions. They provide essential information to constrain cosmic-ray propagation models.

  6. Effects of volatilization on carbon and hydrogen isotope ratios of MTBE.

    PubMed

    Kuder, Tomasz; Philp, Paul; Allen, Jon

    2009-03-15

    Contaminant attenuation studies utilizing CSIA (compound-specific isotope analysis) routinely assume that isotope effects (IEs) result only from degradation. Experimental results on MTBE behavior in diffusive volatilization and dynamic vapor extraction show measurable changes in the isotope ratios of the MTBE remaining in the aqueous or nonaqueous phase liquid (NAPL) matrix. A conceptual model for interpretation of those IEs is proposed, based on the physics of liquid-air partitioning. Normal or inverse IEs were observed for different volatilization scenarios. The range of carbon enrichment factors (epsilon) was from +0.7 per thousand (gasoline vapor extraction) to -1 per thousand (diffusive volatilization of MTBE from gasoline), the range of hydrogen epsilon was from +7 per thousand (gasoline vapor extraction) to -12 per thousand (air sparging of aqueous MTBE). The observed IEs are lower than those associated with MTBE degradation. However, under a realistic scenario for MTBE vapor removal, their magnitude is within the detection limits of CSIA. The potential for interference of those IEs is primarily in confusing the interpretation of samples with a small extent of fractionation and where only carbon CSIA data are available. The IEs resulting from volatilization and biodegradation, respectively, can be separated by combined carbon and hydrogen 2D-CSIA.

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

    SciTech Connect

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

    1989-12-01

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

  8. Carbon and Hydrogen Stable Isotope Fractionation Associated with the Aerobic and Anaerobic Degradation of Saturated and Alkylated Aromatic Hydrocarbons.

    PubMed

    Musat, Florin; Vogt, Carsten; Richnow, Hans H

    2016-01-01

    Saturated hydrocarbons (alkanes) and alkylated aromatic hydrocarbons are abundant environmental compounds. Hydrocarbons are primarily removed from the environment by biodegradation, a process usually associated with moderate carbon and significant hydrogen isotope fractionation allowing monitoring of biodegradation processes in the environment. Here, we review the carbon and hydrogen stable isotope fractionation associated with the cleavage of C-H bonds at alkyl chains of hydrocarbons. Propane, n-butane and ethylbenzene were used as model components for alkyl moieties of aliphatic and aromatic hydrocarbons with emphasis on the cleavage of the C-H bond without the involvement of molecular oxygen. The carbon and hydrogen isotope fractionation factors were further used to explore the diagnostic potential for characterizing the mode of bond cleavage under oxic and anoxic conditions. x039B; factors, calculated to correlate carbon and hydrogen fractionation, allowed to distinguish between aerobic and anaerobic biodegradation processes in the environment.

  9. Solubility of, and hydrogen ion adsorption on, some metal oxides in aqueous solutions to high temperatures

    SciTech Connect

    Palmer, D.A.; Benezeth, P.; Wesolowski, D.J.; Anovitz, L.M.; Machesky, M.L.; Hayashi, Ken-ichiro; Hyde, K.E.

    1997-08-01

    Solubility of boehmite (AlOOH), ferrous hydroxide (Fe(OH)2)/magnetite (Fe3O4), zincite (ZnO), and brucite (Mg(OH)2) were measured over a range of temperatures (AlOOH, 100-290 C; Fe(OH)2/Fe3O4, 100-250 C; ZnO, 50-290 C; Mg(OH)2, 60-200 C) using in situ pH measurements. A hydrogen-electrode concentration cell was used; the pH range depended on the oxide. The solubility results for boehmite mainly demonstrate the method viability, while those for zincite are mainly restricted to mildly acidic to neutral pH where Zn{sup 2+} predominates in solution. The magnetite (presumably coated with Fe(OH)2) solubilities extend from pHs > 5 and, because of relevance to water/steam cycles of power plants, are compared in detail with previous studies. The same cell was used to investigate the surface adsorption-desorption thermodynamics of H ions on rutile (TiO2) and zincite to 290 C. Behavior of pH at zero-point-of-charge as function of temperature and application of the Stern-3-layer model were determined for this solid. The zincite study is still incomplete; preliminary results show trends that can be rationalized only qualitatively now with the zero- point-of-charge being apparently affected by hydration of the surface in basic solutions and specific adsorption of Na ions under the same conditions.

  10. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    NASA Astrophysics Data System (ADS)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the o