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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. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Oxidation of hydrogen isotopes over honeycomb catalysts

    NASA Astrophysics Data System (ADS)

    Munakata, Kenzo; Wajima, Takaaki; Hara, Keisuke; Wada, Kohei; Shinozaki, Yohei; Katekari, Kenichi; Mochizuki, Kazuhiro; Tanaka, Masahiro; Uda, Tatsuhiko

    2011-10-01

    In the process of development of D-T fusion power reactors, recovery of tritium released into the last confinement system would be a key issue related to safety. If an accidental leakage of tritium takes place in a fusion power plant, a large volume of air should be detritiated with an air cleanup system (ACS). In ACS, tritium gas is converted to tritiated water vapor with a catalyst bed, and then which is recovered with an adsorption bed. In this study, the authors examined the applicability of honeycomb-type catalysts to ACS. A screening test of catalysts for oxidation of hydrogen and deuterium was performed using various honeycomb-type and pebble-type catalysts. Experimental results reveal that a honeycomb-type catalyst possesses a high oxidation performance for oxidation of hydrogen isotopes. Furthermore, the isotope effect on the oxidation of hydrogen isotopes over the honeycomb-type catalyst was thoroughly examined and quantified using tritium.

  10. 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. PMID:16852056

  11. 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.

  12. 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.

  13. Hydrogen and helium adsorption on potassium

    SciTech Connect

    Garcia, R.; Mulders, N.; Hess, G.

    1995-04-01

    A previous quartz microbalance study of adsorption of helium on sodium indicates that the inert layer is surprisingly small. Similar experiments with hydrogen on sodium show layer by layer growth below a temperature of 7K. These results motivated the authors to extend the experiments to lower temperatures. A suitable apparatus, capable of reaching 0.45 K, while still enabling them to do in situ alkali evaporation, has been constructed. The authors will report on the results of microbalance adsorption experiments of helium and hydrogen on potassium.

  14. 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.

  15. Interactions of hydrogen isotopes and oxides with metal tubes

    SciTech Connect

    Longhurst, G. R.; Cleaver, J.

    2008-07-15

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

  16. 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.

  17. 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.

  18. 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).

  19. 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

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

    DOEpatents

    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. 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

  2. CoP for hydrogen evolution: implications from hydrogen adsorption.

    PubMed

    Hu, Guoxiang; Tang, Qing; Jiang, De-En

    2016-09-14

    Cobalt phosphide (CoP) is one of the most promising, earth-abundant electrocatalysts discovered to date for hydrogen evolution reaction (HER), yet the mechanism is not well understood. Since hydrogen adsorption is a key factor of HER activity, here we examine the adsorption of atomic hydrogen on the low-Miller-index surfaces of CoP, including (111), (110), (100), and (011), by using periodic density functional theory. From the calculated Gibbs free energy of adsorption, we predict that (111), (110), and (011) surfaces will have good catalytic activities for HER. From ab initio atomistic thermodynamics, we find that the stabilities of the surfaces at 1 atm H2 and 300 K follow the trend of (111) > (100) ∼ (110) ≫ (011). On the most stable (111) surface, both Co bridge sites and P top sites are found to be able to adsorb hydrogen with a close-to-zero free energy change and the synergy of proximal Co and P atoms on the surface results in a better HER activity. Our work provides important insights into CoP's excellent HER activity and a basis for further mechanistic understanding of HER on CoP and other transition-metal phosphides. PMID:27524281

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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

  8. Normalization of oxygen and hydrogen isotope data

    USGS Publications Warehouse

    Coplen, T.B.

    1988-01-01

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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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. PMID:25162630

  15. Toward magnetic trapping of isotopes of hydrogen

    NASA Astrophysics Data System (ADS)

    Clark, Robert; Libson, Adam; Bannerman, S. Travis; Mazur, Thomas; Chavez, Isaac; Raizen, Mark

    2010-03-01

    Over the past decades, spectroscopy of atomic hydrogen has enabled precision measurements of many fundamental physical quantities. Today, the trapping of hydrogen and its isotopes remains an important goal in physics. One promising technique for obtaining such samples is magnetic deceleration of a supersonic beam, via an ``atomic coilgun.'' In this work, we present progress toward magnetically trapping deuterium in a simple room-temperature apparatus, which includes the coilgun and a solid-state laser system for addressing the 1S-2S transition. We also discuss prospects for cooling samples of hydrogen, deuterium, and tritium through the recently discovered technique of single-photon cooling.

  16. 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.

  17. Progress towards trapping of atomic hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Chavez, Isaac; Libson, Adam; Mazur, Tom; Majors, Julia; Raizen, Mark

    2009-05-01

    Using a series of pulsed electromagnetic coils (atomic coilgun) we can stop supersonic beams of paramagnetic atoms and molecules. We will employ the coilgun method to stop and trap supersonic beams of hydrogen isotopes. The slowed atoms will be trapped in a quadrupole magnetic trap where single-photon atomic cooling will be applied. Further applications will be discussed.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Hydrogen Isotope Behavior in Type 316 Stainless Steel Sorbed by Various Methods

    SciTech Connect

    Oya, Y.; Onishi, Y.; Okuno, K.; Kawano, T.; Asakura, Y.; Uda, T.; Tanaka, S.

    2005-07-15

    Typical materials for components, type 316 stainless steel (316-SS), were chosen as a sample and hydrogen isotope was charged by various methods, water adsorption, electrolysis and ion irradiation to elucidate hydrogen isotope behavior on/in SS. The chemical states of SS surface were studied by XPS and the hydrogen isotope retention and its desorption behavior were analyzed by TDS. Two types of surface finish, namely non-pretreated sample and pretreated sample by polish and annealing were prepared. It was found that the oxy-hydroxide and hydroxide were formed on the surface layer. The hydrogen isotope desorption stages consisted of three stages, namely the desorption stages from oxy-hydroxide, hydroxide and bulk hydrogen. A large amount of deuterium was trapped by the oxy-hydroxide layer for the non-pretreated sample with electrolysis. The hydrogen isotope trapping by this layer would have a large influence on the hydrogen isotope retention. The surface finish would be one of the effective improvement for decreasing its retention on SS.

  4. Toward magnetic trapping of isotopes of hydrogen

    NASA Astrophysics Data System (ADS)

    Clark, Robert; Bannerman, S. Travis; Chavez, Isaac; Libson, Adam; Mazur, Tom; Raizen, Mark

    2010-03-01

    Over the past decades, spectroscopy of atomic hydrogen has enabled precision measurements of many fundamental physical quantities. While atomic hydrogen has previously been trapped, its heavier isotopes deuterium and tritium have not. One promising technique for obtaining these samples is magnetic deceleration of a supersonic beam, via an ``atomic coilgun.'' In this work, we present progress toward magnetically trapping deuterium in a simple room-temperature apparatus, which includes the coilgun and a solid-state laser system for addressing the 1S-2S transition. We also discuss prospects for cooling samples of deuterium and tritium through the recently discovered technique of single-photon cooling.

  5. 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.

  6. 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.

  7. 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.

  8. Adsorption of hydrogen on boron-doped graphene: A first-principles prediction

    SciTech Connect

    Zhou, Yungang; Zu, Xiaotao T.; Gao, Fei; Nie, JL; Xiao, H. Y.

    2009-01-01

    The doping effects of boron on the atomic adsorption of hydrogen on graphene have been investigated using density functional theory calculations. The hydrogen adsorption energies and electronic structures have been considered for pristine and B-doped graphene with the adsorption of hydrogen on top of carbon or boron atom. It is found that the B-doping forms an electron-deficient structure, and decreases the hydrogen adsorption energy dramatically. For the adsorption of hydrogen on top of other sites, similar results also have been found. These results indicate that the hydrogen storage capacity is improved by the doping of B atom.

  9. 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

  10. Hydrogen isotope composition of magmatic water

    SciTech Connect

    Taylor, B.E. )

    1992-01-01

    Isotopic tracing of H[sub 2]O degassing in both small and very large rhyolitic magmas in continental tectonic settings (USA and New Zealand), and isotopic studies of high-temperature fumaroles (USA, Japan, and elsewhere) indicate that the hydrogen isotope compositions of magmatic waters vary primarily with the composition of source material and tectonic setting. Water from felsic magmas in volcanic arc settings has a mean [delta]D value off [minus]25 [+-] 5 permil, whereas water from volcanic and plutonic magmas in continental settings has a slightly lower mean [delta]D of [minus]40 [+-] 10 permil. These differences reflect the variation in composition of source materials: hydrated oceanic crust and marine sediments for the arc volcanoes, and largely metamorphic crust for magmas in continental settings. The isotopic record in certain ore deposits associated with felsic magmas (e.g., W skarns, Sn-W veins) and geothermal systems records the influx at critical times of magmatic water with a [delta]D value of [minus]35 to [minus]45 permil. This is best documented where isotopic contrast between magmatic and meteoric waters is large. The [delta]D of MORB H[sub 2]O presumably lies between the mean [delta]D for MORB glass ([minus]75 permil), the [delta]D of H[sub 2]O in equilibrium with this glass ([delta]D ca. [minus]35; assuming closed-system degassing).

  11. Hydrogen adsorption of ruthenium: Isosteres of solubility of adsorbed hydrogen

    SciTech Connect

    Zaginaichenko, S.Y.; Matysina, Z.A.; Schur, D.V.; Pishuk, V.K.

    1998-12-31

    The theoretical investigation of solubility isosteres of adsorbed hydrogen has been performed for free face (0001) of crystals with hexagonal close-packed lattice A3 of Mg type. The face free energy has been calculated and its dependence on temperature, pressure, hydrogen concentration and character of hydrogen atoms distribution over surface interstitial sites of different type has been defined. The equations of thermodynamic equilibrium and solubility of adsorbed hydrogen have been defined. The plots of isosteres in the region of phase transition from isotropic to anisotropic state have been constructed and it has been established that in anisotropic state the order in distribution of hydrogen atoms over interstitial sites of different type must become apparent. Comparison of the theoretical isosteres with experimental for ruthenium has been carried out, the isotropic-anisotropic state transition can stipulate a stepwise and break-like change in isosteres.

  12. 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.

  13. 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.

  14. 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.

  15. Detection of Hydrogen Spillover in Palladium-Modified Activated Carbon Fibers During Hydrogen Adsorption

    SciTech Connect

    Contescu, Cristian I; Brown, Craig; Liu, Yun; Bhat, Vinay V; Gallego, Nidia C

    2009-01-01

    Palladium-modified activated carbon fibers (Pd-ACF) are being evaluated for adsorptive hydrogen storage at near-ambient conditions because of their enhanced hydrogen uptake in comparison to Pd-free activated carbon fibers (ACF). The net uptake enhancement (at room temperature and 20 bar) is in excess of the amount corresponding to formation of Pd hydride, and is usually attributed to hydrogen spillover. In this paper, inelastic neutron scattering was used to demonstrate the formation of new C-H bonds in Pd-containing activated carbon fibers after exposure to hydrogen at 20 oC and 1.6 MPa, at the expense of physisorbed H2. This finding is a post-factum proof of the atomic nature of H species formed in presence of a Pd catalyst, and of their subsequent spillover and binding to the carbon support. Chemisorption of hydrogen may explain the reduction in hydrogen uptake from first to second adsorption cycle.

  16. DFT modelling of hydrogen sulphide adsorption on α-Cr2O3 (0001) surface

    NASA Astrophysics Data System (ADS)

    Maldonado, Frank; Stashans, Arvids

    2016-05-01

    Density functional theory has been used to predict properties of hydrogen sulphide, H2S, adsorption on the α-Cr2O3 (0001) surface. Five energetically most favourable adsorption configurations have been selected for the study. Our work reveals adsorption geometries as well as discusses electronic and magnetic properties of the adsorbate on chromium oxide surface. It is shown that two different adsorption types, namely molecular adsorption and dissociative adsorption, can take place leading to two sets of adsorption energies. The most favourable arrangement is found to correspond to the case of dissociative adsorption with molecular hydrogen forming OH group at the α-Cr2O3 (0001) surface.

  17. Water-hydrogen isotope exchange process analysis

    SciTech Connect

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

    2008-07-15

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

  18. 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).

  19. 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

  20. 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.

  1. 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

  2. Hydrogen Adsorption in Carbon-Based Materials Studied by NMR

    NASA Astrophysics Data System (ADS)

    Wu, Yue; Kleinhammes, Alfred; Anderson, Robert; Mao, Shenghua

    2007-03-01

    Hydrogen adsorption in carbon-based materials such as boron-doped graphite and boron-doped single-walled carbon nanotubes (SWNTs) were investigated by nuclear magnetic resonance (NMR). ^1H NMR is shown to be a sensitive and quantitative probe for detecting adsorbed gas molecules such as H2, methane, and ethane. NMR measurements were carried out in-situ under given H2 pressure up to a pressure of over 100 atm. From such ^1H NMR measurement, the amount of adsorbed H2 molecules was determined versus pressure. This gives an alternative method for measuring the adsorption isotherms where the H2 signature is identified based on spin properties rather than weight or volume as in gravimetric and volumetric measurements. The measurement shows that boron doping has a favorable effect on increasing the adsorption enthalpy of H2 in carbon-based systems. This work was done in collaboration with NREL and Department of Chemistry, University of Pennsylvania, within the DOE Center of Excellence on Carbon-based Hydrogen Storage Materials and is supported by DOE.

  3. 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.

  4. 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)

  5. Hydrogen in vanadium: Site occupancy and isotope effects

    NASA Astrophysics Data System (ADS)

    Xin, Xiao; Johansson, Robert; Wolff, Max; Hjörvarsson, Björgvin

    2016-04-01

    We discuss the influence of site occupancy on the absorption of the hydrogen isotopes H and D in thin V(001) layers. By growing V(001) under biaxial compressive strain in Fe/V(001) superlattices, the hydrogen (H as well as D) is forced to reside exclusively in octahedral (Oz) sites, even at the lowest concentrations. A weakening of the isotope effects is observed when hydrogen resides in octahedral as compared to tetrahedral sites.

  6. Coulomb deexcitation of muonic hydrogen in collisions with atoms of hydrogen isotopes

    SciTech Connect

    Kravtsov, A.V.; Mikhailov, A.I.

    1995-05-01

    The asymptotic theory of nonadiabatic transitions is used to treat Coulomb deexcitation of muonic hydrogen in hydrogen, including the effect of electron shielding of the charge of the target nucleus. The rates are calculated for an isotopically pure target and for a mixture of hydrogen isotopes. For a mixture of isotopes the rates of direct and inverse charge exchange with deexcitation are also calculated. 13 refs., 3 figs., 6 tabs.

  7. 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.

  8. 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.

  9. 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.

  10. Hydrogen adsorption in an interpenetrated dynamic metal-organic framework.

    PubMed

    Chen, Banglin; Ma, Shengqian; Zapata, Fatima; Lobkovsky, Emil B; Yang, Jun

    2006-07-24

    A metal-organic framework Zn(NDC)(4,4'-Bpe)(0.5).xG [NDC = 2,6-naphthalenedicarboxylate; 4,4'-Bpe = 4,4'-trans-bis(4-pyridyl)ethylene; G = guest molecules] has been synthesized, structurally characterized, and rationalized to be a two-interpenetrated elongated primitive cubic net. Powder X-ray diffraction and adsorption studies reveal the dynamic feature of the framework, which can take up hydrogen of about 2.0 wt % at 77 K and 40 bar and 0.3 wt % at 298 K and 65 bar. PMID:16841969

  11. Hydrogen adsorption and anomalous electronic properties of nitrogen-doped graphene

    SciTech Connect

    Fujimoto, Yoshitaka; Saito, Susumu

    2014-04-21

    We investigate hydrogen adsorption effects on stabilities and electronic properties of nitrogen defects in graphene using first-principles electronic-structure calculations within the density-functional theory. We find that the adsorption of hydrogen atoms on the pyridine-type nitrogen defects in graphene becomes energetically favorable, whereas in the case of the substitutional nitrogen defect the hydrogen adsorption becomes unfavorable. We also find that a transition from p-type to n-type doping properties occurs by hydrogen adsorption on the pyridine-type defects, suggesting that even the carrier type is controllable in nitrogen-doped graphene.

  12. 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.

  13. 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.

  14. 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.

  15. Negligible Isotopic Effect on Dissociation of Hydrogen Bonds.

    PubMed

    Ge, Chuanqi; Shen, Yuneng; Deng, Gang-Hua; Tian, Yuhuan; Yu, Dongqi; Yang, Xueming; Yuan, Kaijun; Zheng, Junrong

    2016-03-31

    Isotopic effects on the formation and dissociation kinetics of hydrogen bonds are studied in real time with ultrafast chemical exchange spectroscopy. The dissociation time of hydrogen bond between phenol-OH and p-xylene (or mesitylene) is found to be identical to that between phenol-OD and p-xylene (or mesitylene) in the same solvents. The experimental results demonstrate that the isotope substitution (D for H) has negligible effects on the hydrogen bond kinetics. DFT calculations show that the isotope substitution does not significantly change the frequencies of vibrational modes that may be along the hydrogen bond formation and dissociation coordinate. The zero point energy differences of these modes between hydrogen bonds with OH and OD are too small to affect the activation energy of the hydrogen bond dissociation in a detectible way at room temperature. PMID:26967376

  16. Reversible adsorption of hydrogen chloride to ice surfaces

    NASA Astrophysics Data System (ADS)

    Zimmermann, Stefan; Kippenberger, Matthias; Crowley, John

    2015-04-01

    Hydrogen chloride is the most important reservoir of gaseous, reactive chlorine in the atmosphere. Although several laboratory investigations of the interaction of HCl with ice surfaces have been conducted, there is still great uncertainty associated with the adsorption isotherms of HCl on ice, which is largely a consequence of most previous studies being unable to work at concentrations relevant for the atmosphere and to explore the non-saturated part of the isotherm at sub-monolayer coverage. We have conducted experiments on HCl uptake on ice surfaces at temperatures between 190 and 220 K, using a coated wall flow tube. HCl at concentrations as low as 2 × 109 molecule cm3 (~10-8 Torr) was detected using a chemical-ionization, quadrupole mass spectrometer. The equilibrium surface coverage of HCl on ice could be interpreted using the Langmuir-model to derive partition coefficients (KLang). We find that the dissociative Langmuir isotherm describes our data significantly better than the non-dissociative type. Surprisingly, and in contrast to the behavior of the majority of traces-gases which adsorb reversibly on ice surfaces, the partition-coefficients we derive for HCl do not show a systematic dependence on temperature, precluding the simple derivation of an adsorption enthalpy and indicating the presence of more complex adsorption and desorption mechanisms for strong acids ionizing on the surface compared to H-bonded trace gases.

  17. Adsorption of molecular hydrogen on Pd(Pt) decorated graphene

    NASA Astrophysics Data System (ADS)

    Adhikari, Narayan; Khaniya, Asim; Lamichhane, Saran; Pantha, Nurapati

    2015-03-01

    We have performed the first-principles based Density Functional Theory (DFT) calculations to study the stability, geometrical structures, and electronic properties of a Pd(Pt) atom adsorbed graphene to investigate the possibility of using Pd(Pt) decorated graphene as energy storage materials with reference to pristine graphene. The London dispersion forces have been incorporated by the DFT-D2 levels of calculations implemented in Quantum Espresso packages. Our findings show that Pd and Pt both adsorb on graphene at Bridge site. The electronic structures of Pd(Pt) adsorbed graphene possesses band gap opening due to breaking of the symmetry of graphene. Further we have studied the adsorption of moelcular hydrogen ((H 2) n , n = 1-7) on the Pd(Pt)-graphene system. The adatom Pd(Pt) enhances the binding energy per hydrogen molecule in Pd(Pt)-graphene system in comparison to that in the pristine graphene. The binding energy per hydrogen molecule of the adatom-graphene system decreases as the number of H 2 molecules increases and finally it saturates to 0.15 eV (0.16 eV) per hydrogen molecule for Pd-graphene (Pt-graphene) systems respectively. ICTP-NET 56/TWAS.

  18. Isotopic composition of hydrogen in insoluble organic matter from cherts

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.

    1991-01-01

    Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

  19. 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.

  20. 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)

  1. Systematic DFT-GGA study of hydrogen adsorption on transition metals

    NASA Astrophysics Data System (ADS)

    Vasić, D.; Ristanović, Z.; Pašti, I.; Mentus, S.

    2011-12-01

    Computational study of hydrogen adsorption on (111) surface of transition metals with face centered cubic (fcc) lattice is reported and the results are compared with available experimental and theoretical data. In addition, dissociative adsorption of hydrogen on Pt(111), Pt(100) and Pt(110) is studied in the range of coverage from 0.25 to 1 monolayer. In the case of Pt(111) preferential adsorption site was found to be three-coordinated fcc-hollow site, while on Pt(100) and Pt(110) surface hydrogen settles on two-coordinated bridge and short bridge site, respectively. Hydrogen adsorption energy was found to decrease with the increasing coverage. Structural changes of studied Pt surfaces upon hydrogen adsorption have been compared with the experimental data existing in the literature and good qualitative agreement has been obtained.

  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. PMID:25815958

  3. 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.

  4. 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. PMID:19253977

  5. Kinetics and mechanisms of hydrogen sulfide adsorption by biochars.

    PubMed

    Shang, Guofeng; Shen, Guoqing; Liu, Liang; Chen, Qin; Xu, Zhiwei

    2013-04-01

    Three different biochars as cost-effective substitutes for activated carbon (AC) were tested for their hydrogen sulfide (H2S) adsorption ability. The biochars were produced from camphor (SC), bamboo (SB), and rice hull (SR) at 400°C by oxygen-limited pyrolysis. The surface area (SA), pH, and Fourier transform infrared spectras of the biochars and AC were compared. The maximum removal rates and the saturation constants were obtained using the Michaelis-Menten-type equation. The three biochars were found to be alkaline, and the SAs of the biochars were much smaller than that of the AC. The H2S breakthrough capacity was related to the local pH within the pore system of the biochar. The order observed in terms of both biochar and AC adsorption capacity was SR>SB>SC>AC. SR efficiently removed H2S within the inlet concentration range of 10-50 μL/L. Biochars derived from agricultural/forestry wastes are a promising H2S adsorbent with distinctive properties. PMID:23455220

  6. Effect of controlled deactivation on the thermochemical characteristics of hydrogen adsorption on skeletal nickel from sodium hydroxide-water solutions

    NASA Astrophysics Data System (ADS)

    Prozorov, D. A.; Lukin, M. V.; Ulitin, M. V.

    2013-04-01

    Differential heats of adsorption in a wide range of surface coverage and maximum amounts of adsorbed hydrogen are determined by adsorption calorimetry on partially deactivated skeletal nickel from aqueous solutions of sodium hydroxide. The effect of the composition of solutions on the values of limiting adsorption and adsorption equilibria of individual forms of hydrogen is shown.

  7. Adsorption of atomic hydrogen at a nanostructured electrode of polyacrylate-capped Pt nanoparticles in polyelectrolyte.

    PubMed

    Markarian, Marie Zabel; El Harakeh, Maysaa; Halaoui, Lara I

    2005-06-16

    Atomic hydrogen electrosorption is reported at crystallite sites of polyacrylate-capped Pt nanoparticles (d = 2.5 +/- 0.6 nm), by assembling nanostructured electrodes of polyacrylate-Pt nanocrystallites layer-by-layer in a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). Cyclic voltammetry in 1 M H2SO4 revealed a strongly adsorbed hydrogen state and a weakly adsorbed hydrogen state assigned to adsorption at (100) and (110) sites of the modified nanocrystallites, respectively. Resolving hydrogen adsorption states signifies that surface capping by the carboxylate groups is not irreversibly blocking hydrogen adsorption sites at the modified Pt nanoparticle surface. Adsorption peak currents increased with increasing the number of layers up to 16 bilayers, indicating the feasibility of nanoparticle charging via interparticle charge hopping and the accessibility of adsorption states within the thickness of the nanoparticle/polyelectrolyte multilayers. Despite similarity in hydrogen adsorption in the cyclic voltammorgrams in 1 M H2SO4, negative shifts in adsorption potentials were measured at the nanocrystallite Pt-polyelectrolyte multilayers relative to a polycrystalline bulk Pt surface. This potential shift is attributed to a kinetic limitation in the reductive hydrogen adsorption as a result of the Pt nanoparticle surface modification and the polyelectrolyte environment. PMID:16852426

  8. 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.

  9. 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)

  10. 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.

  11. 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.

  12. 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

  13. High coverage hydrogen adsorption on the Fe3O4(1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Yu, Xiaohu; Zhang, Xuemei; Wang, Shengguang

    2015-10-01

    Hydrogen adsorption on the A and B termination layers of the Fe3O4(1 1 0) surface at different coverage has been systematically studied by density functional theory calculations including an on-site Hubbard term (GGA + U). The adsorption of hydrogen prefers surface oxygen atoms on both layers. The more stable A layer has stronger adsorption energy than the less stable B layer. The saturation coverage has two dissociatively adsorbed H2 on the A layer, and one dissociatively adsorbed H2 on the B layer. The adsorption mechanism has been analyzed on the basis of projected density of states (PDOS).

  14. 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).

  15. Sieving hydrogen isotopes through two-dimensional crystals.

    PubMed

    Lozada-Hidalgo, M; Hu, S; Marshall, O; Mishchenko, A; Grigorenko, A N; Dryfe, R A W; Radha, B; Grigorieva, I V; Geim, A K

    2016-01-01

    One-atom-thick crystals are impermeable to atoms and molecules, but hydrogen ions (thermal protons) penetrate through them. We show that monolayers of graphene and boron nitride can be used to separate hydrogen ion isotopes. Using electrical measurements and mass spectrometry, we found that deuterons permeate through these crystals much slower than protons, resulting in a separation factor of ≈10 at room temperature. The isotope effect is attributed to a difference of ≈60 milli-electron volts between zero-point energies of incident protons and deuterons, which translates into the equivalent difference in the activation barriers posed by two-dimensional crystals. In addition to providing insight into the proton transport mechanism, the demonstrated approach offers a competitive and scalable way for hydrogen isotope enrichment. PMID:26721995

  16. Isotopic exchange of hydrogen in aromatic amino acids

    SciTech Connect

    Pshenichnikova, A.B.; Karnaukhova, E.N.; Mitsner, B.I.

    1993-10-20

    The kinetics of the isotopic replacement of hydrogen in the aromatic amino acids L-tryptophan, L-tyrosine, and L-phenylalanine in solutions of deuterochloric and deuterosulfuric acids in deuterium oxide were investigated by PMR spectroscopy. The reactions were shown to be of first orders with respect both to the concentration of the substrate and to the activity of the deuterium ion. The isotopic effects of hydrogen and the values of the activation energy of H-D exchange in different positions of the aromatic ring in tryptophan and tyrosine were determined. The effect of properties of the medium on the rate of the isotopic exchange of hydrogen is discussed. 17 refs., 2 figs., 2 tabs.

  17. 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.

  18. Antiphase hydrogen and oxygen isotope periodicity in chert nodules

    NASA Astrophysics Data System (ADS)

    Sharp, Zachary D.; Durakiewicz, Tomasz; Migaszewski, Zdzislaw M.; Atudorei, Viorel N.

    2002-09-01

    Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial "sigmoidal" periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ 18O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ˜10°C. Data for a second chert fall on a subparallel δD-δ 18O line with δD values that are almost 50‰ lower. The δD-δ 18O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.

  19. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-01-01

    The focus of this project is the combined appication of infrared spectroscopy and stable isotope geochemistry to the study of hydrogen-bearing species dissolved in silicate melts and glasses. We are conducting laboratory experiments aimed at determining the fractionation of D and H between melt species (OH and H{sub 2}O) and hydrous vapor and the diffusivities of these species in glasses and melts. Knowledge of these parameters is critical to understanding the behavior of hydrogen isotopes during igneous processes and hydrothermal processes. These results also could be valuable in application of glass technology to development of nuclear waste disposal strategies.

  20. 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.

  1. 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.

  2. 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.

  3. Molecular simulation of hydrogen adsorption in single-walled carbon nanotubes and idealized carbon slit pores

    NASA Astrophysics Data System (ADS)

    Wang, Qinyu; Johnson, J. Karl

    1999-01-01

    The adsorption of hydrogen gas into single-walled carbon nanotubes (SWNTs) and idealized carbon slit pores is studied by computer simulation. Hydrogen-hydrogen interactions are modeled with the Silvera-Goldman potential. The Crowell-Brown potential is used to model the hydrogen-carbon interactions. Calculations include adsorption inside the tubes, in the interstitial regions of tube arrays, and on the outside surface of isolated tubes. Quantum effects are included through implementation of the path integral formalism. Comparison with classical simulations gives an indication of the importance of quantum effects for hydrogen adsorption. Quantum effects are important even at 298 K for adsorption in tube interstices. We compare our simulations with experimental data for SWNTs, graphitic nanofibers, and activated carbon. Adsorption isotherms from simulations are in reasonable agreement with experimental data for activated carbon, but do not confirm the large uptake reported for SWNTs and nanofibers. Although the adsorption potential for hydrogen in SWNTs is enhanced relative to slit pores of the same size, our calculations show that the storage capacity of an array of tubes is less than that for idealized slit pore geometries, except at very low pressures. Ambient temperature isotherms indicate that an array of nanotubes is not a suitable sorbent material for achieving DOE targets for vehicular hydrogen storage.

  4. 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.

  5. 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.

  6. POSSIBLE INFLUENCE OF HYDROGEN CONCENTRATION ON MICROBIAL METHANE STABLE HYDROGEN ISOTOPIC COMPOSITION

    EPA Science Inventory

    Factors affecting the stable hydrogen isotopic composition (6D) of important sources of microbial methane to the atmosphere include oxidation, methanogenic precursor (e.g., acetate vs. CO2/H2), and the 6D of the environmental water. ariations in hydrogen gas concentrations or rat...

  7. Adsorption in gas mass spectrometry. I. Effects on the measurement of individual isotopic species

    NASA Astrophysics Data System (ADS)

    Gonfiantini, Roberto; Valkiers, Staf; Taylor, Philip D. P.; de Bièvre, Paul

    1997-05-01

    The adsorption-desorption process of gas molecules on the walls of the mass spectrometer inlet system was studied in order to assess quantitatively its influence on measurement results. The effects on individual isotopic species in SiF4 measurements required for the re-determination of the Avogadro constant are discussed in this paper, while the effects on isotope amount ratio determinations will be discussed in a companion paper. A model based on the Langmuir adsorption isotherm is developed, which fits well the experimental observations and provides the means to investigate adsorption and desorption kinetics in the inlet system. A parameter called the [`]apparent leak-rate coefficient' is introduced; this represents the relative variation with time of any isotopic species in the inlet system. All the adsorption parameters appearing in the balance equations are derived from the apparent leak-rate coefficient. Application of the model to long mass-spectrometric measurements of SiF4 yields a rate constant of 6.5 × 10-5 s-1 for SiF4 effusion through the molecular leak of the inlet system. Adsorption and desorption rate-constants are equal to 20-25% of the leak rate-constant, and the adsorption sites are about two orders of magnitude lower than the number of Ni and Cu atoms present on the inlet system walls.

  8. A Transient Model of Induced Natural Circulation Thermal Cycling for Hydrogen Isotope Separation

    SciTech Connect

    SHADDAY, MARTIN

    2005-07-12

    The property of selective temperature dependence of adsorption and desorption of hydrogen isotopes by palladium is used for isotope separation. A proposal to use natural circulation of nitrogen to alternately heat and cool a packed bed of palladium coated beads is under active investigation, and a device consisting of two interlocking natural convection loops is being designed. A transient numerical model of the device has been developed to aid the design process. It is a one-dimensional finite-difference model, using the Boussinesq approximation. The thermal inertia of the pipe walls and other heat structures as well as the heater control logic is included in the model. Two system configurations were modeled and results are compared.

  9. Microscopic Theory of Hysteretic Hydrogen Adsorption in Nanoporous Materials

    SciTech Connect

    Kang, J.; Wei, S. H.; Kim, Y. H.

    2010-01-01

    Understanding gas adsorption confined in nanoscale pores is a fundamental issue with broad applications in catalysis and gas storage. Recently, hysteretic H{sub 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{sub 2} molecules using the MOF Co(1,4-benzenedipyrazolate) [Co(BDP)] as a model system. Using activated H{sub 2} diffusion along the small-pore channels as a dominant equilibration process, we demonstrate that the system shows hysteretic H{sub 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{sub 2} adsorption is an intrinsic adsorption characteristic in the diffusion-controlled small-pore systems.

  10. 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.

  11. 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)

  12. 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.

  13. 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.

  14. 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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  16. Competitive adsorption-driven separation of water/methanol mixtures using hydrogen as a third competitor.

    PubMed

    Lee, Dong-Wook; Yu, Chang-Yeol; Lee, Kew-Ho

    2009-12-01

    In this study, we report competitive adsorption-driven separation of a water/methanol mixture in Pd-deposited silica membranes, which is induced by introducing hydrogen carrier gas as a third competitor. After replacing helium carrier gas by hydrogen carrier gas, water vapor permeance showed a slight decrease, whereas methanol vapor permeance significantly decreased. The water/methanol separation factor remarkably increased from 1.7-16.5 to 6.8-58.2 in the feed water content of 5.8-83.0 wt.%. From single vapor permeation tests in the presence of carrier gas (hydrogen or helium), it was confirmed that those permeation behavior was derived from stronger effect of the competitive adsorption between hydrogen and methanol vapor than that between hydrogen and water vapor. That is, hydrogen carrier gas dominantly inhibits adsorption of methanol vapor on the membrane surface, and the partial pressure of methanol on the membrane surface decreases, which leads to a decrease in methanol permeance with reduced driving force. In addition, temperature programmed desorption (TPD) results of water and methanol from Pd/silica particles also demonstrated that hydrogen carrier gas suppresses methanol adsorption on Pd/silica surface more dominantly than water adsorption. PMID:19772967

  17. 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.

  18. 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.

  19. Determination of the hydrogen isotopic composition of bone collagen and correction for hydrogen exchange

    SciTech Connect

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

    1994-01-01

    The hydrogen isotopic measurement ([delta]D) of the non-exchangeable hydrogens in herbivore bone collagen has potential for paleoclimate research. The authors have developed the methodology for extracting the hydrogen from collagen for isotopic analysis and correcting the [delta]D results for hydrogen exchange. Preparations of whole bone powders, demineralized bone, or gelatin extracts from fresh bone samples all give reliable [delta]D results and have isotopic results, yields, and proportions of exchangeable hydrogens consistent with that expected for collagen. Gelatin extraction for removal of contaminants remains a valuable option for the study of fossil bone samples. Vacuum preheating under good vacuum at 150[degrees]C for two days for whole bone powders and at 100[degrees]C for one day for gelatins is an important step to remove all adsorbed water before samples are oxidized for isotopic analysis. Of the remaining hydrogens released following oxidation, 20.5% in whole bone powders and 23.1% in gelatin extracts exchange with laboratory atmospheric water vapor within 48 hours. The [delta]D results can be corrected for this exchange and for minor effects of sample preparation by using a calibration bone standard to determine the [delta]D value of laboratory water vapor.

  20. 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.

  1. Adsorption and dissociation of molecular hydrogen on the (0001) surface of double hexagonal close packed americium

    NASA Astrophysics Data System (ADS)

    Dholabhai, P. P.; Ray, A. K.

    2009-01-01

    Hydrogen molecule adsorption on the (0001) surface of double hexagonal packed americium has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals method (FP-L/APW+lo). Weak molecular hydrogen adsorptions were observed. Adsorption energies were optimized with respect to the distance of the adsorbates from the surface for three approach positions at three adsorption sites, namely t1 (one-fold top), b2 (two-fold bridge), and h3 (three-fold hollow) sites. Adsorption energies were computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at the fully relativistic level (with spin-orbit coupling SOC). The most stable configuration corresponds to a horizontal adsorption with the molecular approach being perpendicular to a lattice vector. The surface coverage is equivalent to one-fourth of a monolayer (ML), with the adsorption energies at the NSOC and SOC theoretical levels being 0.0997 eV and 0.1022 eV, respectively. The respective distance of the hydrogen molecule from the surface and hydrogen-hydrogen distance was found to be 2.645 Å and 0.789 Å, respectively. The work functions decreased and the net magnetic moments remained almost unchanged in all cases compared with the corresponding quantities of bare dhcp Am (0001) surface. The adsorbate-substrate interactions have been analyzed in detail using the partial charges inside the muffin-tin spheres, difference charge density distributions, and the local density of states. The effects of adsorption on the Am 5f electron localization-delocalization characteristics have been discussed. Reaction barrier for the dissociation of hydrogen molecule has been presented.

  2. Isotopic fractionation during soil uptake of atmospheric hydrogen

    NASA Astrophysics Data System (ADS)

    Rice, A.; Dayalu, A.; Quay, P.; Gammon, R.

    2011-03-01

    Soil uptake of atmospheric hydrogen (H2) and the associated hydrogen isotope effect were studied using soil chambers in a Western Washington second-growth coniferous forest. Chamber studies were conducted during both winter and summer seasons to account for large natural variability in soil moisture content (4-50%) and temperature (6-22 °C). H2 deposition velocities were found to range from 0.01-0.06 cm s-1 with an average of 0.033 ± 0.008 cm s-1 (95% confidence interval). Consistent with prior studies, deposition velocities were correlated with soil moisture below 20% soil moisture content during the summer season. During winter, there was considerable variability observed in deposition velocity that was not closely related to soil moisture. The hydrogen kinetic isotope effect with H2 uptake was found to range from -24‰ to -109‰. Aggregate analysis of experimental data results in an average KIE of -57 ± 5‰ (95% CI). Some of the variability in KIE can be explained by larger isotope effects at lower (<10%) and higher (>30%) soil moisture contents. The measured KIE was also found to be correlated with deposition velocity, with smaller isotope effects occurring at higher deposition velocities. If correct, these findings will have an impact on the interpretation of atmospheric measurements and modeling of δD of H2.

  3. Isotopic fractionation during soil uptake of atmospheric hydrogen

    NASA Astrophysics Data System (ADS)

    Rice, A.; Dayalu, A.; Quay, P.; Gammon, R.

    2010-11-01

    Soil uptake of atmospheric hydrogen (H2) and the associated hydrogen isotope effect were studied using soil chambers in a Western Washington second-growth coniferous forest. Chamber studies were conducted during both winter and summer seasons to account for large natural variability in soil moisture content (4-50%) and temperature (6-22 °C). H2 deposition velocities were found to range from 0.01-0.06 cm s-1 with an average of 0.033 ± 0.008 cm s-1 (95% confidence interval). Consistent with prior studies, deposition velocities were correlated with soil moisture below 20% soil moisture content during the summer season. Considerable variability in deposition velocity observed during winter was not found to be closely related to soil moisture. The hydrogen kinetic isotope effect with H2 uptake was found to range from -24‰ to -109‰. Aggregate analysis of experimental data results in an average KIE of -57 ± 5‰ (95% CI). Some of the variability in KIE can be explained by larger isotope effects at lower (<10%) and higher (>30%) soil moisture contents. The measured KIE was also found to be correlated with deposition velocity, with smaller isotope effects occurring at higher deposition velocities. If correct, these findings will have an impact on the interpretation of atmospheric measurements and modeling of δD of H2.

  4. 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.

  5. Structures of seven molybdenum surfaces and their coverage dependent hydrogen adsorption.

    PubMed

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

    2016-02-17

    Systematic density functional theory calculations and ab initio atomistic thermodynamics were applied to investigate the stability of seven metallic Mo surfaces [(110), (211), (111), (321), (310), (210) (100)] and their coverage dependent hydrogen adsorption. Only dissociative hydrogen adsorption is favored on these surfaces up to more than one monolayer saturation coverage. The computed hydrogen desorption temperatures on Mo(100) at 500 K and on Mo(110) at 410 K are in agreement with the available temperature-programmed desorption results. Under the consideration of H2 as the reduction reagent in Mo catalyst preparation, the computed surface morphology of Mo single crystal shows only exposed (110), (211) and (100) at high temperature; and the estimated surface proportion order of (110) > (211) > (100) agrees very well with the X-ray diffraction detected intensity order of (110) > (211) > (100). Surface reconstruction upon hydrogen adsorption has also been discussed. PMID:26838012

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

    SciTech Connect

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

    2010-03-11

    A simple hydrogen adsorption measurement system utilizing the volumetric differential pressure technique has been designed, fabricated and calibrated. Hydrogen 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 be helpful in understanding the adsorption property of the studied carbon materials using the fundamentals of adsorption theory. The principle of the system follows the Sievert-type method. 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 operating pressure of the pressure transducer is 20 bar and calibrated with an accuracy of +-0.01 bar. High purity hydrogen is being used in the system and the amount of samples for the study is between 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 the adsorption process by eliminating the errors caused by temperature expansion effects and other non-adsorption related phenomena. The ideal gas equation of state is applied to calculate the hydrogen adsorption capacity based on the differential pressure measurements. Activated carbon with a surface area of 644.87 m{sup 2}/g showed a larger amount of adsorption as compared to multiwalled nanotubes (commercial) with a surface area of 119.68 m{sup 2}/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

  7. 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.

  8. Mechanism of enhanced hydrogen adsorption on palladium-doped nanoporous carbon fibers

    SciTech Connect

    Contescu, Cristian I; Gallego, Nidia C; Wu, Xianxian; Tekinalp, Halil; Edie, Dan; Thies, Mark C; Baker, Frederick S

    2007-01-01

    Recent work at Oak Ridge National Laboratory was directed towards adsorptive storage of hydrogen in nanoporous carbon fibers in which palladium was incorporated prior to spinning and carbonization/activation of the fibers. Palladium doped carbon fibers exhibited enhanced hydrogen uptake compared to the corresponding palladium-free nanoporous carbon fibers (at room temperature and 2 MPa pressure). However, the mechanism responsible for the enhanced hydrogen uptake is not fully understood. New findings are presented in this paper in support of a mechanism that encompasses both hydrogen spillover on palladium metal sites and hydrogen physisorption on nanostructured carbon sites.

  9. 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.

  10. 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.

  11. Heavy hydrogen isotopes penetration through austenitic and martensitic steels

    NASA Astrophysics Data System (ADS)

    Dolinski, Yu.; Lyasota, I.; Shestakov, A.; Repritsev, Yu.; Zouev, Yu.

    2000-12-01

    Experimental results are presented of deuterium and tritium permeability through samples of nickel, austenitic steel (16Cr-15Ni-3Mo-Ti), and martensitic steel DIN 1.4914 (MANET) exposed to a gaseous phase. Experiments were carried out at the RFNC-VNHTF installation, which has the capability of measuring the permeability of hydrogen isotopes by mass spectrometry over a temperature range of 293-1000 K, hydrogen isotope pressure ranges of 50-1000 Pa. Sample disks (30 and 40 mm diam.) can be assembled in the test chamber by electron-beam welding or mounted (30-mm diam. disks) on gaskets. Diffusion and permeability dependencies on temperature and pressure are determined and corresponding activation energies are presented.

  12. 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

  13. 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.

  14. Calculation of hydrogen isotopic fractionations in biogeochemical systems

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Hayes, John M.

    2005-02-01

    Hydrogen-isotopic data are often interpreted using mathematical approximations originally intended for other isotopes. One of the most common, apparent in literature over the last several decades, assumes that delta values of reactants and products are separated by a constant fractionation factor: δ p = δ r + ɛ p/r. Because of the large fractionations that affect hydrogen isotopes, such approximations can lead to substantial errors. Here we review and develop general equations for isotopic mass balances that include the differential fractionation of each component in a mixture and discuss their use in three geochemical applications. For the fractionation of a single component, the reactant and product are related by δ p = α p/rδ r + ɛ p/r, where α and ɛ refer to the same fractionation. Regression of δ p on δ r should give equivalent fractionations based on the intercept and slope, but this has not generally been recognized in studies of D/H fractionation. In a mixture of two components, each of which is fractionated during mixing, there is no unique solution for the three unknown variables (two fractionation factors and the elemental mixing ratio of the two hydrogen sources). The flow of H from CH 4 and H 2O to bacterial lipids in the metabolism of Methylococcus capsulatus provides an example of such a case. Data and conclusions from an earlier study of that system (Sessions et al., 2002) are reexamined here. Several constraints on the variables are available based on plausible ranges for fractionation factors. A possible refinement to current experimental procedures is the measurement of three different isotopes, which would allow unique determination of all variables.

  15. 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.

  16. 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)

  17. 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.

  18. Hydrogen adsorption on palladium: a comparative theoretical study of different surfaces

    NASA Astrophysics Data System (ADS)

    Dong, W.; Ledentu, V.; Sautet, Ph.; Eichler, A.; Hafner, J.

    1998-08-01

    The interaction of atomic hydrogen with the Pd(111), Pd(100) and Pd(110) surfaces is studied by ab-initio density functional calculations within the generalized gradient approximation (GGA). For the three surfaces, we have determined the preferred adsorption sites, the adsorption structures, the work function changes and the surface diffusion barrier, including relaxation effects. This comparative study allows some common features to be seen, in particular in the adsorption energies and geometries for both surface and subsurface H-atoms, and some significant differences such as the surface diffusion and the dispersion of the H-induced surface state. The origin of these differences is explained by a detailed analysis of the electronic structures of both clean and hydrogen-covered surfaces. Our study leads to an interesting correlation between the hydrogen diffusion barrier and the surface roughness since it plays an important part in the catalytic activity of the respective surfaces.

  19. Hydrogen burning of the rare oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Buckner, Matthew Quinn

    2014-10-01

    At the Laboratory for Experimental Nuclear Astrophysics (LENA), two rare oxygen isotope proton capture studies were performed at low energies--- 18O(p,gamma)19F and 17O( p,gamma)18F. The goal of each study was to improve thermonuclear reaction rates at stellar plasma temperatures relevant to 18O and 17O destruction, respectively. The stellar nucleosynthesis temperature regime corresponds to very low proton bombarding energies. At these low energies, the Coulomb barrier suppresses the reaction yield in the laboratory, and environmental backgrounds dominate the detected signal, making it difficult to differentiate the gamma-cascade from background. At LENA, the electron cyclotron resonance (ECR) ion source produces intense, low-energy proton beam, and these high currents boost the reaction yield. LENA, a ``sea-level" facility dedicated to nuclear astrophysics, also has a coincidence detector setup that reduces environmental background contributions and boosts signal-to-noise. The sensitivity afforded by gammagamma-coincidence and high beam current allowed these rare oxygen isotope reactions to be probed at energies that correspond to stellar plasma temperatures. For stars with masses between 0.8 solar masses < M < 8.0 solar masses, nucleosynthesis enters its final phase during the asymptotic giant branch (AGB) stage. This is an evolutionary period characterized by grain condensation that occurs in the stellar atmosphere; the star also experiences significant mass loss during this period of instability. Presolar grain production can often be attributed to this unique stellar environment. A subset of presolar oxide grains features dramatic 18O depletion that can not be explained by the standard asymptotic giant star burning stages and dredge-up models. An extra mixing process for low-mass asymptotic giant branch stars, known as cool bottom processing (CBP), was used in the literature to explain this and other anomalies. Cool bottom processing can also occur during the

  20. 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.

  1. Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Abild-Pedersen, F.; Greeley, J.; Studt, F.; Rossmeisl, J.; Munter, T. R.; Moses, P. G.; Skúlason, E.; Bligaard, T.; Nørskov, J. K.

    2007-07-01

    Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorption energy of the central, C, N, O, or S atom, the scaling constant depending only on x. A model is proposed to understand this behavior. The scaling model is developed into a general framework for estimating the reaction energies for hydrogenation and dehydrogenation reactions.

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

    SciTech Connect

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

    1999-07-10

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

  3. 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.

  4. Hydrogen adsorption in ZIF-7: A DFT and ab-initio molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Dixit, Mudit; Major, Dan Thomas; Pal, Sourav

    2016-05-01

    Primary H2 adsorption sites in a zeolitic imidazolate framework, ZIF-7, are identified using ab-initio density functional theory (DFT) based molecular dynamics annealing simulations. The simulations suggest several low energy adsorption sites. The effect of light transition metal decoration on hydrogen storage properties was studied. Our ab-intio DFT calculations illustrate that decorating the ZIF with Sc increases both the number of H2 molecules, as well as the H2 binding energy. The binding energy (∼25 kJ/mol per H2) at 8H2 loading in the pore, suggests that Sc-ZIFs can be potential candidates for hydrogen storage.

  5. 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. PMID:24989118

  6. 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.

  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. 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

  9. 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

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-04-01

    The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 10 4 to 10 8 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ˜75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D 2O

  12. 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)

  13. 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.

  14. Structure sensitive adsorption of hydrogen on ruthenium and ruthenium-silver catalysts supported on silica

    SciTech Connect

    Kumar, N.

    1999-02-12

    Supported metal catalysts typically consist of particles with sizes less than 10 nm, and because of the small crystallite size, low coordination number sites (edges and corners) represent a significant fraction of all surface sites. Furthermore, it has been demonstrated that adsorption rates can be much greater at these low coordination sites than on basal plane sites. What has not been generally appreciated, however, is that preferential adsorption at edge and corner sites may explain the mechanism by which a promoter, or the addition of a second metal to form a bimetallic, can alter the selectivity and rate of reaction. For example, the measurements of hydrogen adsorption onto supported Ru-Ag catalysts show marked decreases in the amount of hydrogen adsorbed relative to the amount adsorbed on Ru catalysts. Although it is known that Ag does not dissociatively adsorb hydrogen, this decrease cannot be explained by a simple one-to-one site blocking mechanism unless Ag preferentially populates edges and corners, thereby reducing the number of Ru edge sites. Indeed, Monte Carlo simulations of Ru-Group IB metal catalysts predict that Group IB metal atoms preferentially populate corner and edge sites of ruthenium crystals. This evidence, taken together, suggests that adsorption occurs preferentially at Ru corner and edge sites, which act as portals onto basal planes. A model based on this portal theory for hydrogen adsorption onto supported ruthenium bimetallic catalysts has been developed using a rate equation approach. Specifically, the model accounts for the following features: (1) preferential adsorption through portals, (2) basal plane site-energy multiplicity, and (3) hydrogen spillover onto the support. A comparison of model predictions with experiment is presented for different concentration of Ag in Ru-Ag catalysts. The portal model of hydrogen adsorption can explain the observed decreased in the amount of hydrogen adsorbed on Ru-Ag catalysts. The model can be

  15. 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. PMID:19928879

  16. 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.

  17. 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.

  18. Adsorption of hydrogen sulfide onto activated carbon fibers: effect of pore structure and surface chemistry.

    PubMed

    Feng, Wenguo; Kwon, Seokjoon; Borguet, Eric; Vidic, Radisav

    2005-12-15

    To understand the nature of H2S adsorption onto carbon surfaces under dry and anoxic conditions, the effects of carbon pore structure and surface chemistry were studied using activated carbon fibers (ACFs) with different pore structures and surface areas. Surface pretreatments, including oxidation and heattreatment, were conducted before adsorption/desorption tests in a fixed-bed reactor. Raw ACFs with higher surface area showed greater adsorption and retention of sulfur, and heat treatment further enhanced adsorption and retention of sulfur. The retained amount of hydrogen sulfide correlated well with the amount of basic functional groups on the carbon surface, while the desorbed amount reflected the effect of pore structure. Temperature-programmed desorption (TPD) and thermal gravimetric analysis (TGA) showed that the retained sulfurous compounds were strongly bonded to the carbon surface. In addition, surface chemistry of the sorbent might determine the predominant form of adsorbate on the surface. PMID:16475362

  19. Metastable polymorphs of hydrogen isotopes solidified near the triple point

    NASA Astrophysics Data System (ADS)

    Kozioziemski, B. J.; Chernov, A. A.; Mapoles, E. R.; Sater, J. D.

    2010-07-01

    Hydrogen (H2) , deuterium (D2) , and the 0.25D2-0.5DT-0.25T2 isotopic mixture of deuterium and tritium (D-T) each form a metastable solid state below their respective triple-point temperatures (TTP) . The metastable solid is observed to nucleate and grow from inside of a 5-10μm inner diameter borosilicate glass tube when the liquid hydrogens are slowly cooled through their respective TTP . These metastable solids have their triple-point temperature 15-43 mK below the stable hexagonal close-packed (hcp) crystal of the same composition, a different growth habit, and recrystallize to the hcp solid. This metastable solid may be a crystal with unknown structure or, less likely, hcp with stacking faults and other defects.

  20. Modeling hydrogen isotope behavior in fusion plasma-facing components

    NASA Astrophysics Data System (ADS)

    Hu, Alice; Hassanein, Ahmed

    2014-03-01

    In this work, we focus on understanding hydrogen isotope retention in plasma-facing materials in fusion devices. Three common simulation methods are usually used to study this problem that includes Monte Carlo, molecular dynamics, and numerical/analytical methods. A system of partial differential equations describing deuterium behavior in tungsten under various conditions is solved numerically to explain recent data compared to other methods. The developed model of hydrogen retention in metals includes classic, intercrystalline and trapped-induced Gorsky effects. The bombardment and depth profile of 200 eV deuterium in single crystal tungsten are simulated and compared with recent work. The total deuterium retention at various temperatures and fluences are also calculated and compared with available data. The results are in reasonable agreement with data and therefore, this model can be used to estimate deuterium inventory and recovery in future fusion devices.

  1. 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.

  2. 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.

  3. 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.

  4. Effect of previous fertilization on phosphorus adsorption. Measurement of surface phosphorus by isotopic exchange

    SciTech Connect

    Lopez, S.C.; Barbaro, N.O.; De Tramontini, S.R. )

    1990-09-01

    Adsorption properties of a soil with previous additions of different phosphate fertilizers were characterized by means of the Langmuir isotherm. The best correlation with the Langmuir isotherm was obtained for low added-phosphorus concentration and for conditions of different amounts of initial soil phosphorus treatment. The phosphorus initially present in each soil sample was evaluated by isotopic exchange. (The use of different isotopic methodologies is discussed.) Carrier-free {sup 32}P was added to a soil-solution system in adsorption equilibrium after soil agitation with increasing phosphorus concentration solutions for 5 days; this allowed measurement of the adsorbed phosphorus that remained exchangeable phosphorus and equilibrium phosphorus concentration was found. The surface exchangeable phosphorus concentration at 0.3 ppm was used to estimate initial surface soil phosphorus. Taking these corrections into account, the authors found adsorption maximum and the bonding energy constant were similar in spite of the amount and kind of previous fertilizer addition. However, the behavior of superphosphate seemed to be modified in the presence of rock phosphate, especially in relation to exchange ability.

  5. 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

  6. 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.

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

    DOE PAGESBeta

    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

  8. Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

    NASA Astrophysics Data System (ADS)

    Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

    2015-05-01

    Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation

  9. Unrestricted density functional study on the adsorption of hydrogen molecule on nickel surface

    NASA Astrophysics Data System (ADS)

    Ishiwatari, Ryo; Tachikawa, Masanori

    2005-02-01

    The adsorption of hydrogen molecule on Ni(100) and (111) surfaces is studied by unrestricted hybrid density functional calculation. Ni6 and Ni8 clusters are used as small single layer models, while Ni13 cluster as a model containing the second layer. The total energy of triplet state is most stable for both Ni6 (100) fourfold and Ni8 (111) threefold sites. We have found that the optimized geometrical parameters become closer to the experimental values, as the multiplicity increases from singlet to quintet states. Our adsorption energy on Ni13 (100) bridge site gives in reasonable agreement with the experimental value.

  10. Adsorption interaction in the molecular hydrogen-aluminophosphate AlPO-5 zeolite system

    NASA Astrophysics Data System (ADS)

    Grenev, I. V.; Gavrilov, V. Yu.

    2015-03-01

    The adsorption interaction between molecular hydrogen and atoms forming the lattice of AlPO-5 zeolite is studied. The potential of intramolecular interaction is calculated by summing the potentials of individual pairwise H2-O(Al, P) interactions in a fragment of the zeolite structure with a volume of ˜32 nm3. Isopotential surfaces are constructed that allow determination of the shape of zeolite microchannels and the places of the preferential localization of sorbate molecules in the porous space. The calculated and experimental values of the Henry constant of H2 adsorption on AlPO-5 at 77 K are compared.

  11. 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.

  12. 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.

  13. Adsorption of nucleobase pairs on hexagonal boron nitride sheet: hydrogen bonding versus stacking.

    PubMed

    Ding, Ning; Chen, Xiangfeng; Wu, Chi-Man Lawrence; Li, Hui

    2013-07-14

    The adsorption of hydrogen-bonded and stacked nucleobase pairs on the hexagonal boron nitride (h-BN) surface was studied by density functional theory and molecular dynamics methods. Eight types of nucleobase pairs (i.e., GG, AA, TT, CC, UU, AT, GC, and AU) were chosen as the adsorbates. The adsorption configurations, interaction energies, and electronic properties of the nucleobase pair on the h-BN surface were obtained and compared. The density of states analysis result shows that both the hydrogen-bonded and stacked nucleobase pairs were physisorbed on h-BN with minimal charge transfer. The hydrogen-bonded base pairs lying on the h-BN surface are significantly more stable than the stacked forms in both the gas and water phase. The molecular dynamics simulation result indicates that h-BN possessed high sensitivity for the nucleobases and the h-BN surface adsorption could revert the base pair interaction from stacking back to hydrogen bonding in aqueous environment. The h-BN surface could immobilize the nucleobases on its surface, which suggests the use of h-BN has good potential in DNA/RNA detection biosensors and self-assembly nanodevices. PMID:23689542

  14. 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.

  15. Combined adsorption and oxidation mechanisms of hydrogen sulfide on granulated coal ash.

    PubMed

    Asaoka, Satoshi; Hayakawa, Shinjiro; Kim, Kyung-Hoi; Takeda, Kazuhiko; Katayama, Misaki; Yamamoto, Tamiji

    2012-07-01

    Hydrogen sulfide is highly toxic to benthic organisms and may cause blue tide with depletion of dissolved oxygen in water column due to its oxidation. The purpose of this study is to reveal the combined adsorption and oxidation mechanisms of hydrogen sulfide on granulated coal ash that is a byproduct from coal electric power stations to apply the material as an adsorbent for hydrogen sulfide in natural fields. Sulfur species were identified in both liquid and solid phases to discuss removal mechanisms of the hydrogen sulfide with the granulated coal ash. Batch experiments revealed that hydrogen sulfide decreased significantly by addition of the granulated coal ash and simultaneously the sulfate ion concentration increased. X-ray absorption fine structure analyses showed hydrogen sulfide was adsorbed onto the granulated coal ash and successively oxidized by manganese oxide (III) contained in the material. The oxidation reaction of hydrogen sulfide was coupling with reduction of manganese oxide. On the other hand, iron containing in the granulated coal ash was not involved in hydrogen sulfide oxidation, because the major species of iron in the granulated coal ash was ferrous iron that is not easily reduced by hydrogen sulfide. PMID:22487226

  16. Hydrogen isotope exchange experiments with Mt Mazama ash

    NASA Astrophysics Data System (ADS)

    Nolan, G. S.; Bindeman, I. N.; Palandri, J. L.

    2011-12-01

    The 2H/H ratio in hydrous minerals and volcanic glass are routinely used as paleo proxies to infer ∂2H value of meteoric waters and thus paleo-climate conditions. There is a widely held assumption that once environmental water is taken up by the ash to ~3-4 wt%, hydrogen isotopes preserve original hydrologic environmental conditions through time. We report a series of 2H -H aqueous exposure experiments of 7600BP Mt Mazama ash from the Crater Lake eruption. Native Mt. Mazama ash, ~69% SiO2 contains ~3.75% H2O with ∂2H -145 %. Water exposure experiments for this ash were done at 70, 40 and 25°C, time from 0 to >7000 h, to evaluate rates of hydrogen uptake from deuterated waters (650 % to pure D2O). Measurements were performed on 1-2 mg of ash using TCEA-MAT253 GSMS. We also employ a KBr pellet technique with infrared spectroscopy to measure total water and molecular water peaks. In this fashion an estimation of the distribution of water vs. SiOH is possible. Time series experiments aided by infrared measurements demonstrate the following new results: 1) Depending on exposure time and temperature we observe 5 to >100 % 2H uptake in dried samples positively correlated with temperature. In as little as 48 hours approximately 5% ∂2H increases are seen in samples incubated at 70 °C with 650 % water. At this rate the ash at 70 °C would take ~2.9 years to fully react with 2H. Other separate samples reacted with pure D2O develop a clear infrared signal at ~ 2600 cm-1 due to OD bond stretching. 2) Step heating experiments on native ash indicate the ∂2H of the remaining water does not change until the ash is heated to past 200-220 °C. 3) A sample immersed in 650 % ∂2H water for >300 days at 70 °C degassed and sampled at increasing temperature intervals as above shows an enrichment ranging from 250 % at no water lost to 20 % at .10 % water when compared to native ash. 4) Ash dried under vacuum at ~130 °C shows mostly (~80%) loss of molecular water accompanied by

  17. 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.

  18. 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.

  19. 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. Modeling played an important role throughout the project. For example, we used molecular simulations to determine that

  20. 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. PMID:16688311

  1. Surface studies of metals after interaction with hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Silver, David Samuel

    1998-12-01

    The objective of this research is to characterize surfaces of metals after interaction with hydrogen isotopes. Iron, which does not readily bond with hydrogen, and palladium, which strongly bonds with hydrogen, were studied. Observations of surfaces are used to determine the nature of their metamorphosis due to such exposures. An experimental study of pure iron foil (99.99%) exposed to a hot, dense hydrogen and argon gas mixture in a ballistic compressor yielded evidence for new structural and compositional changes of the metal due to the exposure. Atomic force microscope (AFM) studies demonstrated surfaces to be highly uneven, where height variations were often 2 mum for many micron-sized regions scanned. An iron foil exposed to argon gases alone revealed unique dendritic patterns but negligible height variations for micron-size scans. A cold rolled single crystal palladium cathode was electrolyzed in a solution of Dsb2O and 15% Hsb2SOsb4 by volume for 12 minutes. The cathode bent toward the anode during electrolysis. Examination of both concave and convex surfaces using the scanning electron microscope (SEM), scanning tunneling microscope (STM), and AFM revealed rimmed craters with faceted crystals inside and multi-textured surfaces. Also pairs of cold rolled polycrystalline palladium cathodes underwent electrolysis for six minutes or less, in Dsb2O and Hsb2O solutions, each solution containing 15% Hsb2SOsb4, by volume. Surface morphologies of the heavy water electrolyzed samples revealed asperities, craters, and nodules, and evidence of recrystallization and crystal planes. After 1.5 years, new AFM studies of the same Pd surfaces exposed to heavy water electrolyte exhibited loose, nanometer-sized particles. However, the surfaces of Pd cathodes exposed to light water electrolyte remained nearly identical to morphologies of foils not electrolyzed, and did not change with time. No surface asperities or loose grains were observed on the latter. Secondary ion mass

  2. 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. PMID:26717417

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

    PubMed

    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. PMID:27211517

  4. Effect of metal and nonmetal on adsorption of hydrogen in torus-type C120

    NASA Astrophysics Data System (ADS)

    Zhou, Caihua; Ma, Ning; Fan, Guang; Ma, Zhanying

    2016-02-01

    The hydrogen adsorption properties for the torus-type C120, and the changes of adsorption influenced by nonmetal and metal have been systematically investigated. The results show that, in the pristine torus-type C120, the inner carbon atoms have more negative static potential than the outer ones. H2 intends to accumulate at the area near inner carbon atoms. However, torus-type C120 is modified by nonmetal (N and O) or metal (Li), the accumulated fields of H2 are changed. Li can evidently enhance the hydrogen storage capacity. The most gravimetric density is predicted to be 7.21 wt% for the 8Li-C120 in 77 K and 1200 kPa.

  5. NEST-GENERATION TCAP HYDROGEN ISOTOPE SEPARATION PROCESS

    SciTech Connect

    Heung, L; Henry Sessions, H; Anita Poore, A; William Jacobs, W; Christopher Williams, C

    2007-08-07

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

  6. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules.

    PubMed

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

    2016-08-19

    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 H_{2}/D_{2} 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 H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation. PMID:27588855

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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. PMID:20681605

  12. 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.

  13. Retention of Hydrogen Isotopes in Neutron Irradiated Tungsten

    SciTech Connect

    Yuji Hatano; Masashi Shimada; Yasuhisa Oya; Guoping Cao; Makoto Kobayashi; Masanori Hara; Brad J. Merrill; Kenji Okuno; Mikhail A. Sokolov; Yutai Katoh

    2013-03-01

    To investigate the effects of neutron irradiation on hydrogen isotope retention in tungsten, disk-type specimens of pure tungsten were irradiated in the High Flux Isotope Reactor in Oak Ridge National Laboratory followed by exposure to high flux deuterium (D) plasma in Idaho National Laboratory. The results obtained for low dose n-irradiated specimens (0.025 dpa for tungsten) are reviewed in this paper. Irradiation at coolant temperature of the reactor (around 50 degrees C) resulted in the formation of strong trapping sites for D atoms. The concentrations of D in n-irradiated specimens were ranging from 0.1 to 0.4 mol% after exposure to D plasma at 200 and 500 degrees C and significantly higher than those in non-irradiated specimens because of D-trapping by radiation defects. Deep penetration of D up to a depth of 50-100 µm was observed at 500 degrees C. Release of D in subsequent thermal desorption measurements continued up to 900 degrees C. These results were compared with the behaviour of D in ion-irradiated tungsten, and distinctive features of n-irradiation were discussed.

  14. Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Young, A. F.; Nittler, L. R.; Alexander, C. M. O'D

    2004-01-01

    Hydrogen isotopes are highly variable among primitive meteorites and interplanetary dust particles (IDPs) [1, 2]. In particular, many primitive objects exhibit D (and N-15) enrichments, relative to terrestrial values, thought to represent partial preservation of presolar material fractionated in molecular clouds. However, the diversity of D/H ratios among IDPs and chondrites indicates a complex history of processing in the solar nebula and on meteorite parent bodies. Deconvolving this record requires identification and characterization of the carriers of D enrichments in different objects. Isotopic imaging has proven to be a powerful method to quantitatively explore the distribution of D/H ratios on a one to several m scale in IDPs [2-4] and the CR chondrite Renazzo [5, 6]. In this study, we have used ion imaging to explore the microscale D/H distribution of two carbonaceous chondrites, Tagish Lake (unique) and Al Rais (CR2). Previous D/H measurements (on a tens of microns scale) of Tagish Lake matrix fragments by Messenger [7] and Engrand et al. [8] have found different results, most likely related to the analytical techniques used. Previous work has also shown a large range of D/H ratios in CR chondrites, including very large variations on a scale of a few microns [5, 6, 9].

  15. Energetic, crystallographic and diffusion characteristics of hydrogen isotopes in iron

    NASA Astrophysics Data System (ADS)

    Sivak, A. B.; Sivak, P. A.; Romanov, V. A.; Chernov, V. M.

    2015-06-01

    Energetic, crystallographic and diffusion characteristics of various interstitial configurations of H atoms and their complexes with self-point defects (SIA - self-interstitial atom, V - vacancy) in bcc iron have been calculated by molecular statics and molecular dynamics using Fe-H interatomic interaction potential developed by Ramasubramaniam et al. (2009) and modified by the authors of the present work and Fe-Fe matrix potential M07 developed by Malerba et al. (2010). The most energetically favorable configuration of an interstitial H atom is tetrahedral configuration. The energy barrier for H atom migration is 0.04 eV. The highest binding energy of all the considered complexes "vacancy - H atom" and "SIA - H atom" is 0.54 and 0.15 eV, respectively. The binding energy of H atom with edge dislocations in slip systems <1 1 1>{1 1 0}, <1 1 1>{1 1 2}, <1 0 0>{1 0 0}, <1 0 0>{1 1 0} is 0.32, 0.30, 0.45, 0.54 eV, respectively. The binding energy of H atom in VHn complexes (n = 1 … 15) decreases from 0.54 to 0.35 eV with increasing of n from 1 to 6. At n > 6, it decreases to ∼0.1 eV. The temperature dependences of hydrogen isotopes (P, D, T) diffusivities have been calculated for the temperature range 70-1800 K. Arrhenius-type dependencies describe the calculated data at temperatures T < 100 K. At T > 250 K, the temperature dependencies of the diffusivities DP, DD, DT have a parabolic form. The diffusivities of H isotopes are within 10% at room temperature. The isotope effect becomes stronger at higher temperatures, e.g., ratios DP/DD and DP/DT at 1800 K equal 1.23 and 1.40, respectively.

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

    PubMed

    Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; 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 H2 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 H2 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. PMID:24329077

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. [Research on the experiment of hydrogen isotope fractionation using diamond anvil cell and Raman spectra].

    PubMed

    Wang, Shi-xia; Zheng, Hai-fei

    2011-03-01

    Hydrothermal diamond-anvil cell and Raman spectroscopy were used to measure the hydrogen isotope fractionation factor between gypsum and liquid water. Hydrogen isotopes of deuterium (D) and hydrogen (H) show the largest relative mass difference in all stable isotope systems. The exchange reaction between D and H would easily take place and the extent of exchange would be larger than others under same condition. So we selected the hydrogen isotopes for the investigation. The concept of fractionation factor is the quotient of ratios of heavy and light isotopes in different minerals, and can be expressed as alpha(A-B) = R(A)/R(B). There is a linear relationship between ratio of Raman peak intensities and ratio of corresponding amount of substances. So the fractionation factor between gypsum and heavy water can be expressed as [formula: see text] The experimental study for the isotope fractionation is based on the dissolution and recrystallization of minerals in aqueous solutions. The process can reach the total isotope fractionation equilibrium and get isotope fractionation factors with different temperatures. Compared with other methods, chemical synthesis one has following advantages: (1) short time for the experiment; (2) no problem about the equilibrium for isotope exchanges. It was proved that the new method would be more convenient and reliable for obtaining the isotopic fractionation factor compared with previous ways. PMID:21595220

  4. Solubility, diffusivity, and isotopic exchange rate of hydrogen isotopes in Li-Pb

    SciTech Connect

    Maeda, Y.; Edao, Y.; Yamaguchi, S.; Fukada, S.

    2008-07-15

    The diffusion, solution and permeation coefficients of hydrogen isotopes in liquid Li-Pb which is a candidate liquid blanket material for fusion reactors were determined in the temperature range 573-973 K using an unsteady permeation method. Each coefficients was correlated to temperature as follows: D{sub Li-Pb} = 1.8 x 10{sup -8} exp(-11590/RT) [m{sup 2}/s] (1) K{sub Li-Pb} = 2.1x10{sup -6} exp(-18700/RT) [1/Pa{sup 0.5}] (2) P{sub Li-Pb} = 1.8x10{sup -9} exp(-30290/RT) [mol/msPa{sup 0.5}] (3) The hydrogen permeation flux depends on the square root of pressure at 773-973 K. Although the power of pressure declined below 0.4 when temperature was below 673 K, the effects of surface resistance were neglected above 673 K. The hydrogen solubility in liquid Li-Pb was found to correlate with a Sievert's constant. We calculated a height-equivalent to theoretical-plate of a gas-liquid countercurrent extraction tower for tritium recovery rates in liquid Li-Pb to be H{sub L}= 7.0x10{sup -2} [m] (4). (authors)

  5. Experimental investigations of trimer ion contributions in the low resolution mass spectrometry of hydrogen isotope mixtures.

    PubMed

    Bidica, Nicolae

    2012-01-01

    This paper reports on some preliminary experimental results of a work in progress regarding a problem involving the quantitative analysis of hydrogen isotopes by mass spectrometry of low resolution: the triatomic (trimer) ions interferences with the isotopic hydrogen species having the same mass/charge. These results indicate that, in complex mixtures of hydrogen isotopes, trimer ions are strongly affected by the presence of other species, and a new approach that takes into account the destruction mechanism of trimer ions is necessary for a proper determination of their contributions. PMID:23149602

  6. 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)

  7. 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.

  8. Assessing The Hydrogen Adsorption Capacity Of Single-Wall Carbon Nanotube / Metal Composites

    NASA Astrophysics Data System (ADS)

    Heben, Michael J.; Dillon, Anne C.; Gilbert, Katherine E. H.; Parilla, Philip A.; Gennett, Thomas; Alleman, Jeffrey L.; Hornyak, G. Louis; Jones, Kim M.

    2003-07-01

    Carefully controlled and calibrated experiments indicate a maximum capacity for adsorption of hydrogen on SWNTs is ˜8 wt% under room temperature and pressure conditions. Samples displaying this maximum value were prepared by sonicating purified SWNTs in a dilute nitric acid solution with a high-energy probe. The process cuts the SWNT into shorter segments and introduces a Ti-6Al-4V alloy due to the disintegration of the ultrasonic probe. The Ti-6Al-4V alloy is a well-known metal hydride and its contribution to the measured hydrogen uptake was accounted for in order to assess the amount of hydrogen stored on the SWNT fraction. The principal purpose of this paper is to present key details associated with the measurement procedures in order to illustrate the degree of rigor with which the findings were obtained.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. Reconstructing a Hot and High Eocene Sierra Nevada Using Oxygen and Hydrogen Isotopes in Kaolinite

    NASA Astrophysics Data System (ADS)

    Mix, H.; Ibarra, D. E.; Mulch, A.; Graham, S. A.; Chamberlain, C. P.

    2014-12-01

    Despite the broad interest in determining the topographic and climatic histories of mountain ranges, the evolution of California's Sierra Nevada remains actively debated. Prior stable isotope-based studies of Sierra Nevada have relied exclusively on hydrogen isotopes in kaolinite, hydrated volcanic glass and leaf n-alkanes. Additional constraints from the oxygen isotope composition of phyllosilicates increase the robustness of findings from a single isotope system and allow for the reconstruction of paleotemperatures. Here, we reconstruct the temperature and elevation of the Early Eocene Sierra Nevada using the oxygen isotope composition of kaolinitized granite clasts from the ancestral Yuba and American Rivers. We evaluate the possible contributions of hydrogen isotope exchange by direct comparison with more robust oxygen isotope measurements. Next, we utilize differences in the hydrogen and oxygen isotope fractionation in kaolinite to constrain paleotemperature. Oxygen isotope geochemistry of in-situ kaolinites indicates upstream (eastward) depletion of 18O in the northern Sierra Nevada. δ18O values ranging from 11.4 - 14.4 ‰ at the easternmost localities correspond to paleoelevations as high as 2400 m when simulating the orographic precipitation of moisture from a Pacific source using Eocene boundary conditions. This finding is consistent with stable isotope studies of the northern Sierra, but oxygen isotope based paleoelevation estimates are systematically ~500 - 1000 m higher than those from hydrogen-based estimates from the same samples. Kaolinite geothermometry from 16 samples measured in duplicate or triplicate produce an average Early Eocene temperature of 24.2 ± 2.0 °C (1s). This kaolinite temperature reconstruction is in agreement with paleofloral and geochemical constraints and general circulation model simulations from Eocene California. Our results confirm prior hydrogen isotope-based paleoelevations and further substantiate the existence of a

  14. Hydrogen Adsorption, Dissociation and Diffusion on the α-U(001) Surface

    SciTech Connect

    Nie, JL; Xiao, H. Y.; Zu, Xiaotao T.; Gao, Fei

    2008-11-05

    First-principles pseudopotential plane wave calculations based on density functional theory and the generalized gradient approximation have been used to study the adsorption, dissociation, and diffusion of hydrogen on the α-U(001) surface. Weak molecular chemisorption was observed for H2 approaching with its molecular axis parallel to the surface. The optimization of the adsorption geometries on the threefold hollow sites yields final configurations with H2 molecules move towards the top site at both coverages of 0.25 and 0.5 monolayer. A low dissociation barrier of 0.081 eV was determined for H2 dissociated from onefold top site with the H atoms falling into the two adjacent threefold hollow sites. The density of states analysis along the dissociation paths show that the hybridization of U 5f and H 1s states only occurs when H2 molecule is dissociated.

  15. 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.

  16. Selective adsorption of atomic hydrogen on a h-BN thin film

    SciTech Connect

    Koswattage, Kaveenga Rasika; Shimoyama, Iwao; Baba, Yuji; Sekiguchi, Tetsuhiro; Nakagawa, Kazumichi

    2011-07-07

    The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the {pi}{sup *} band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational X{alpha} method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen.

  17. Selective adsorption of atomic hydrogen on a h-BN thin film.

    PubMed

    Koswattage, Kaveenga Rasika; Shimoyama, Iwao; Baba, Yuji; Sekiguchi, Tetsuhiro; Nakagawa, Kazumichi

    2011-07-01

    The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the π* band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational Xα method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen. PMID:21744913

  18. 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.

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

    DOE PAGESBeta

    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 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

  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. 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.

  2. 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.

  3. Hydrogen isotope trapping in Al-Cu binary alloys

    DOE PAGESBeta

    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

  4. 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.

  5. 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

  6. Muon transfer from muonic atoms of hydrogen isotopes to He nuclei

    SciTech Connect

    Bystritskii, V.M.

    1995-05-01

    The entire body of experimental results on muon transfer from {mu} atoms of hydrogen isotopes to helium nuclei is discussed and subjected to comparative analysis. A program of further investigations aimed at obtaining more precise and detailed information about the characteristics of {mu}-atomic and {mu}-molecular processes in mixtures of hydrogen isotopes and helium is proposed. 34 refs., 5 figs., 1 tab.

  7. 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.

  8. First-principles study of hydrogen adsorption in metal-doped COF-10

    NASA Astrophysics Data System (ADS)

    Wu, Miao Miao; Wang, Qian; Sun, Qiang; Jena, Puru; Kawazoe, Yoshiyuki

    2010-10-01

    Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H2 molecules. However, at high concentration, Li atoms cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H2 molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.

  9. First-principles study of hydrogen adsorption in metal-doped COF-10

    SciTech Connect

    Wu Miaomiao; Sun Qiang; Wang Qian; Jena, Puru; Kawazoe, Yoshiyuki

    2010-10-21

    Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H{sub 2} molecules. However, at high concentration, Li atoms cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H{sub 2} molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.

  10. First-principles study of hydrogen adsorption in metal-doped COF-10

    NASA Astrophysics Data System (ADS)

    Wu, M. M.; Wang, Q.; Sun, Q.; Jena, P.; Kawazoe, Y.; Department of Advanced Materials; Nanotechnology, Peking University Team; Department of Physics, Virginia Commonwealth University Collaboration; InstituteMaterials Research, Tohoku University Collaboration

    2011-03-01

    Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H2 molecules. However, at high concentration, Li atoms cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H2 molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.

  11. Electronic structures of hybrid graphene/boron nitride nanoribbons with hydrogen adsorption

    NASA Astrophysics Data System (ADS)

    Lee, Chi-Hsuan; Yang, Chih-Kai

    Electronic properties of hybrid graphene/boron nitride nanoribbons are investigated using density functional calculations. It is found that hydrogen adsorption on a graphene nanoribbon alters band structures drastically. Furthermore, H-vacancy chains and lines can effectively shape the conduction properties. Influences of edge atoms with nonzero magnetic moments and the interface between B and N are also prominent in the electronic structures. This work was supported by the Ministry of Science and Technology of the Republic of China under Grant Number MOST 104-2112-M-004-003.

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

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2010-09-15

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) 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) δ(2)H reproducibility (1σ 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 LN(2) is used as a moisture trap for gaseous hydrogen. PMID:20718408

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Novel Atomic Rearrangement in the Pb Monolayer on Si(111) surfaces Induced by Atomic Hydrogen Adsorption.

    NASA Astrophysics Data System (ADS)

    Fang, Chung-Kai; Hwang, Ing-Shouh; Chang, Shih-Hsin; Chen, Lih-Juann; Tsong, Tien-Tzou

    2006-03-01

    Using a scanning tunneling microscopy, we have observed interesting hydrogen-adsorption induced atomic rearrangements on Pb/Si(111) system at room temperature. A hexagonal ring-like pattern with decaying intensity is formed around the hydrogen-induced point defect. Moreover, interference-like patterns can be seen in the region among the H-induced point defects. The detailed pattern depends on the relative position of defects. With certain relative positions, a new superstructure of hexagonal cells can be seen. The phase boundaries are found to either enhance or suppress the formation of the hexagonal ring-like pattern. We believe that the intricate interplay between atomic displacement and electronic structure causes the formation of the patterns. [Ref] : I. S. Hwang, S. H. Chang, C. K. Fang, L. J. Chen, and T. T. Tsong, Phys. Rev. Lett. 94, 045505 (2005)

  18. Factors affecting the hydrogen isotopic composition of dissolved organic matter along a salinity gradient

    NASA Astrophysics Data System (ADS)

    Debond, A. A.; Ziegler, S. E.; Fogel, M. L.; Morrill, P. L.; Bowden, R.

    2010-12-01

    The role of terrestrial dissolved organic matter (DOM) in regulating estuarine ecosystem processes is poorly understood, in part due to difficulties in tracking terrestrial DOM in marine environments. Analysis of multiple stable isotopes (C, N, S) is often required due to poor separation of the carbon isotope signatures of marine and terrestrial sources. However, hydrogen isotopes exhibit greater fractionation. Marine DOM sources have a hydrogen isotope signature of 0‰ while terrestrial DOM can have signatures of up to -270‰ at the poles. Some challenges must be addressed before hydrogen isotopes can be used to track terrestrial DOM in aquatic environments. Hydrogen isotopes may undergo exchange between water and organic matter, obscuring terrestrial signatures. Riverine discharge into marine environments introduces terrestrial DOM to water of different chemical and isotopic compositions which could influence the isotopic composition of the terrestrial DOM. We investigate the effects of changes in water isotopic composition on DOM by introducing terrestrial DOM to freshwaters of isotopic compositions up to +1000‰ for up to two months. We also use surface water samples along a salinity transect at the Salmonier Arm, Newfoundland, Canada to investigate the effects of changes in water mass conditions (pH, salinity and water isotopes) on terrestrial DOM. In addition to changes in water mass conditions, methods for isolating estuarine DOM may regulate affect its isotopic composition. Ultrafiltration (UF), a size-exclusion technique, has been shown to isolate and concentrate the largest proportion of DOM in estuarine environments. UF separates DOM into low molecular weight (LMW, <1kDa) and high molecular weight (HMW, >1kDa) fractions. However, under certain processing conditions, some LMW DOM can be retained. During desalting (diafiltration), LMW DOM continues to be removed from the concentrate, whereas HMW DOM is retained. The proportion of LMW DOM retained

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Carbon and hydrogen isotopic compositions of stratospheric methane: 2. Two-dimensional model results and implications for kinetic isotope effects

    NASA Astrophysics Data System (ADS)

    McCarthy, M. C.; Boering, K. A.; Rice, A. L.; Tyler, S. C.; Connell, P.; Atlas, E.

    2003-08-01

    New high-precision measurements of the carbon and hydrogen isotopic compositions of stratospheric CH4 made on whole air samples collected aboard the NASA ER-2 aircraft are compared with results from the Lawrence Livermore National Laboratory 2-D model. Model runs incorporating sets of experimentally determined kinetic isotope effects (KIEs) for the reactions of CH4 with each of the oxidants OH, O(1D), and Cl are examined with the goals of determining (1) how well the 2-D model can reproduce the observations for both the carbon and hydrogen isotopic compositions, (2) what factors are responsible for the observed increase in the apparent isotopic fractionation factors with decreasing methane mixing ratios, and (3) how sensitive the modeled isotopic compositions are to various experimentally determined KIEs. Bound by estimates of the effects of uncertainties in model chemistry and transport on isotopic compositions, we then examine the constraints the ER-2 observations place on values for the KIEs. For the carbon KIE for reaction of CH4 with O(1D), for example, the analysis of model results and observations favors the larger of the experimental values, 1.013, over a value of 1.001. These analyses also suggest that intercomparisons of results from different models using a given set of KIEs may be useful as a new diagnostic of model-model differences in integrated chemistry and transport.

  4. 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

    2016-09-01

    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. PMID:27499230

  5. 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. PMID:26855125

  6. 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.

  7. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    PubMed

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  8. 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

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

    SciTech Connect

    DeNiro, M.J.; Epstein, S.

    1981-12-16

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

  10. First-principles study of oxygen and hydrogen adsorption on Pt(111) and PtML/Pd(111) surfaces

    NASA Astrophysics Data System (ADS)

    Nie, J. L.; Ao, L.; Zu, X. T.

    2015-11-01

    In this paper, first-principles calculations based on density functional theory (DFT) have been performed to investigate the adsorption of oxygen and hydrogen on Pt(111) and Pd(111) surfaces covered by monolayer (ML) of Pt(PtML/Pd(111)). The results have shown that the oxygen molecule tends to adsorb on fcc site on both surfaces at the coverage of 0.25 ML, which becomes degeneration with hcp site when the coverage increases to 1 ML. For both oxygen and hydrogen, the adsorption on PtML/Pd(111) surface are stronger than those on Pt(111) surface. The adsorption energy difference for oxygen on the two surfaces is ˜0.2 eV at the coverage of 1 ML, which increases to ˜0.6 eV with the coverage decreasing to 0.25 ML. The similar energy difference was also found for hydrogen adsorption. The density of states analysis have demonstrated the chemical interaction of adsorbed oxygen with both pure Pt(111) and PtML/Pd(111) surfaces with certain shift of O2p states to lower level compared to isolated oxygen. For hydrogen adsorption, the hybridization of H1s with Pt5d states were observed for both surfaces, indicating the covalent bonding component of H-Pt bond.

  11. 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.

  12. 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. PMID:22160758

  13. 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.

  14. Hydrogen isotopes in individual alkenones from the Chesapeake Bay estuary

    NASA Astrophysics Data System (ADS)

    Schwab, Valérie F.; Sachs, Julian P.

    2011-12-01

    Hydrogen isotope ratios of individual alkenones from haptophyte algae were measured in suspended particles and surface sediment from the Chesapeake Bay (CB) estuary, eastern USA, in order to determine their relationship to water δD values and salinity. δD values of four alkenones (MeC 37:2, MeC 37:3, EtC 38:2, EtC 38:3) from particles and sediments were between -165‰ and -221‰ and increased linearly ( R2 = 0.7-0.9) with water δD values from the head to the mouth of the Bay. Individual alkenones were depleted in deuterium by 156-188‰ relative to water. The MeC 37 alkenones were consistently enriched by ˜12‰ relative to the EtC 38 alkenones, and the di-unsaturated alkenones of both varieties were consistently enriched by ˜20‰ relative to the tri-unsaturated alkenones. All of the increase in alkenone δD values could be accounted for by the water δD increase. Consequently, no net change in alkenone-water D/ H fractionation occurred as a result of the salinity increase from 10 to 29. This observation is at odds with results from culture studies with alkenone-producing marine coccolithophorids, and from two field studies, one with a dinoflagellate sterol in the CB, and one with a wide variety of lipids in saline ponds on Christmas Island, that indicate a decline in D/ H fractionation with increasing salinity. Why D/ H fractionation in alkenones in the CB showed no dependence on salinity, while D/ H fractionation in CB dinsoterol decreased by 1‰ per unit increase in salinity remains to be determined. Two hypotheses we consider to be valid are that (i) the assemblage of alkenone-producing haptophytes changes along the Bay and each species has a different sensitivity to salinity, such that no apparent trend in αalkenone-water occurs along the salinity gradient, and (ii) greater osmoregulation capacity in coastal haptophytes may result in a diminished sensitivity of alkenone-water D/ H fractionation to salinity changes.

  15. 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

  16. Hydrogen isotope fractionation in lipids of the methane-oxidizing bacterium Methylococcus capsulatus

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Jahnke, Linda L.; Schimmelmann, Arndt; Hayes, John M.

    2002-11-01

    Hydrogen isotopic compositions of individual lipids from Methylococcus capsulatus, an aerobic, methane-oxidizing bacterium, were analyzed by hydrogen isotope-ratio-monitoring gas chromatography-mass spectrometry (GC-MS). The purposes of the study were to measure isotopic fractionation factors between methane, water, and lipids and to examine the biochemical processes that determine the hydrogen isotopic composition of lipids. M. capsulatus was grown in six replicate cultures in which the δD values of methane and water were varied independently. Measurement of concomitant changes in δD values of lipids allowed estimation of the proportion of hydrogen derived from each source and the isotopic fractionation associated with the utilization of each source. All lipids examined, including fatty acids, sterols, and hopanols, derived 31.4 ± 1.7% of their hydrogen from methane. This was apparently true whether the cultures were harvested during exponential or stationary phase. Examination of the relevant biochemical pathways indicates that no hydrogen is transferred directly (with C-H bonds intact) from methane to lipids. Accordingly, we hypothesize that all methane H is oxidized to H 2O, which then serves as the H source for all biosynthesis, and that a balance between diffusion of oxygen and water across cell membranes controls the concentration of methane-derived H 2O at 31%. Values for α l/ w, the isotopic fractionation between lipids and water, were 0.95 for fatty acids and 0.85 for isoprenoid lipids. These fractionations are significantly smaller than those measured in higher plants and algae. Values for α l/ m, the isotopic fractionation between lipids and methane, were 0.94 for fatty acids and 0.79 for isoprenoid lipids. Based on these results, we predict that methanotrophs living in seawater and consuming methane with typical δD values will produce fatty acids with δD between -50 and -170‰, and sterols and hopanols with δD between -150 and -270‰.

  17. 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.

  18. Modeling of temporal behavior of isotopic exchange between gaseous hydrogen and palladium hydride power

    SciTech Connect

    Melius, C F; Foltz, G W

    1987-01-01

    A parametric rate-equation model is described which depicts the time dependent behavior of the isotopic exchange process occurring between the solid and gas phases in gaseous hydrogen (deuterium) flows through packed-powder palladium deuteride (hydride) beds. The exchange mechanism is assumed to be rate-limited by processes taking place on the surface of the powder. The fundamental kinetic parameter of the model is the isotopic exchange probability, p, which is the probability that an isotopic exchange event occurs during a collision of a gas phase atom with the surface. Isotope effects between the gas and solid phases are explicitly included in terms of the isotope separation factor, ..cap alpha... Results of the model are compared with recent experimental measurements of isotope exchange in the ..beta..-phase hydrogen/palladium system and, using a literature value of ..cap alpha.. = 2.4, a good description of the experimental data is obtained for p approx. 10/sup -7/. In view of the importance of the isotope effects in the hydrogen/palladium system and the range of ..cap alpha.. values reported for the ..beta..-phase in the literature, the sensitivity of the model results to a variation in the value of ..cap alpha.. is examined.

  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

    2007-06-01

    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. PMID:17627319

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

    PubMed

    Koehler, Geoff; Wassenaar, Leonard I

    2012-04-17

    Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed. PMID:22432837

  1. 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.

  2. 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.

  3. Effects of heat-treatment and hydrogen adsorption on Graphene grown on Cu foil

    NASA Astrophysics Data System (ADS)

    Cho, Jongweon; Gao, Li; Tian, Jifa; Cao, Helin; Yu, Qingkai; Guest, Jeffrey; Chen, Yong; Guisinger, Nathan

    2011-03-01

    Graphene has recently been a subject of intense research efforts due to its remarkable physical properties as an ideal two-dimensional material. While numerous different methods for graphene synthesis are being explored, CVD-grown graphene on Cu foil presents the possibility of a large-scale and high-quality synthesis of graphene.[1] To improve the quality of graphene films on Cu foil prepared by CVD and better understand its microscopic growth, atomic-scale characterization becomes of great importance. We have investigated the effects of thermal annealing and hydrogen adsorption/desorption on ex-situ CVD-grown monolayer graphene on polycrystalline Cu foil at the atomic-scale using ultrahigh vacuum scanning tunneling microscopy, and we will report on these studies.

  4. New template for metal decoration and hydrogen adsorption on graphene-like C 3N 4

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Sun, Hong; Chen, Changfeng

    2009-07-01

    From density functional theory calculations we identify a graphene-like C 3N 4 (g-C 3N 4) as an excellent template for stable and well dispersed decoration of alkali (Li) and 3 d transition metal (TM) atoms. The porous sites of g-C 3N 4 accommodate excessive N lone-pair electrons and promote hybridization between the orbitals of N and the metal atoms. The most stable TM decorations (Ti and Sc) on g-C 3N 4 exhibit high capacities of hydrogen adsorption with binding energies suitable for mobile applications. These metal decorated g-C 3N 4 may also prove useful in catalytic and sensing applications for their unique nanoscale structural features unavailable in conventional nano-clusters.

  5. 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).

  6. 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).

  7. 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.

  8. 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.

  9. Density functional study of manganese atom adsorption on hydrogen-terminated armchair boron nitride nanoribbons

    NASA Astrophysics Data System (ADS)

    Abdullahi, Yusuf Zuntu; Rahman, Md. Mahmudur; Shuaibu, Alhassan; Abubakar, Shamsu; Zainuddin, Hishamuddin; Muhida, Rifki; Setiyanto, Henry

    2014-08-01

    In this paper, we have investigated stable structural, electric and magnetic properties of manganese (Mn) atom adsorption on armchair hydrogen edge-terminated boron nitride nanoribbon (A-BNNRs) using first principles method based on density-functional theory with the generalized gradient approximation. Calculation shows that Mn atom situated on the ribbons of A-BNNRs is the most stable configuration, where the bonding is more pronounced. The projected density of states (PDOS) of the favored configuration has also been computed. It has been found that the covalent bonding of boron (B), nitrogen (N) and Mn is mainly contributed by s, d like-orbitals of Mn and partially occupied by the 2p like-orbital of N. The difference in energy between the inner and the edge adsorption sites of A-BNNRs shows that Mn atoms prefer to concentrate at the edge sites. The electronic structures of the various configurations are wide, narrow-gap semiconducting and half-metallic, and the magnetic moment of Mn atoms are well preserved in all considered configurations. This has shown that the boron nitride (BN) sheet covered with Mn atoms demonstrates additional information on its usefulness in future spintronics, molecular magnet and nanoelectronics devices.

  10. Effectiveness and mechanisms of hydrogen sulfide adsorption by camphor-derived biochar.

    PubMed

    Shang, Guofeng; Shen, Guoqing; Wang, Tingting; Chen, Qin

    2012-08-01

    The characteristics and mechanisms of hydrogen sulfide (H2S) adsorption on a biochar through pyrolysis at various temperatures (100 to 500 degrees C) were investigated. The biochar used in the current study was derived from the camphor tree (Cinnamomum camphora). The samples were ground and sieved to produceparticle sizes of 0.4 mm to 1.25 mm, 0.3 mm to 0.4 mm, and <0.3 mm. The H2S breakthrough capacity was measured using a laboratory-designed test. The surface properties of the biochar were characterized using pH and Fourier-transform infrared spectroscopy (FTIR) analysis. The results obtained demonstrate that all camphor-derived biochars were effective in H2S sorption. Certain threshold ranges ofthepyrolysis temperature and surfacepH were observed, which, when exceeded, have dramatic effects on the H2S adsorption capacity. The sorption capacity ranged from 1.2 mg/g to 121.4 mg/g. The biochar with 0.3 mm to 0.4 mm particle size possesses a maximum sorption capacity at 400 degrees C. The pH and FTIR analysis results showed that carboxylic and hydroxide radical groups were responsible for H2S sorption. These observations will be helpful in designing biochar as engineered sorbents for the removal of H2S. PMID:22916434

  11. 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.

  12. 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

  13. 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. "

  14. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses. Progress report

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-03-01

    The focus of this project is the combined appication of infrared spectroscopy and stable isotope geochemistry to the study of hydrogen-bearing species dissolved in silicate melts and glasses. We are conducting laboratory experiments aimed at determining the fractionation of D and H between melt species (OH and H{sub 2}O) and hydrous vapor and the diffusivities of these species in glasses and melts. Knowledge of these parameters is critical to understanding the behavior of hydrogen isotopes during igneous processes and hydrothermal processes. These results also could be valuable in application of glass technology to development of nuclear waste disposal strategies.

  15. 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.

  16. FLOSHEET: microcomputerized flowsheeting/simulation program for simulating hydrogen isotope separation processes

    SciTech Connect

    Busigin, A.; Sepa, T.R.; Sood, S.K.

    1987-01-01

    Ontario Hydro has developed a comprehensive computer program, FLOSHEET, to simulate various hydrogen isotope separation processes, including water distillation and cryogenic distillation of elemental hydrogen isotopes. FLOSHEET was developed to assist in the operation and optimization of a Tritium Removal Facility Ontario Hydro is building at the Darlington Nuclear Generating Station. However, FLOSHEET is a general purpose simulator and allows the specification and simulation of complete process plants with various interconnected units. This paper discusses the development and features of FLOSHEET, as well as various simulation results which have emerged from the use of the program.

  17. 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

  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. 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.

  20. 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. PMID:25746007

  1. 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. PMID:27142478

  2. Role of hydrogen in SiH{sub 2} adsorption on Si(100)

    SciTech Connect

    Hong, S.; Chou, M.Y.

    1998-11-01

    When disilane (Si{sub 2}H{sub 6}) is used in the homoepitaxial growth of Si by chemical vapor deposition (CVD), the fragment SiH{sub 2} is believed to be the basic unit adsorbed on the surface. The bonding site of SiH{sub 2} on Si(100) has been proposed in the literature to be either on top of a dimer (the on-dimer site) or between two dimers in the same row (the intrarow site). Since the pathway of SiH{sub 2} combination is dependent on the adsorption site, a first-principles calculation will shed light on the underlying process. We have performed self-consistent pseudopotential density-functional calculations within the local-density approximation. On the bare Si(100) surface, the on-dimer site is found to be more stable than the intrarow site, even though the former has unfavorable Si-Si bond angles. This is ascribed to the extra dangling bond created in the latter geometry when the weak dimer {pi} bonds are broken. However, the presence of hydrogen adatoms eliminates this difference and makes the intrarow site more favorable than the on-dimer site. It is therefore revealed in this theoretical study that hydrogen, an impurity unavoidable in the CVD process, plays an important role in determining the stable configuration of adsorbed SiH{sub 2} on Si(100) and hence affects the growth mechanism. {copyright} {ital 1998} {ital The American Physical Society}

  3. Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials.

    PubMed

    Schüth, Christoph; Taubald, Heinrich; Bolaño, Nerea; Maciejczyk, Kirsten

    2003-07-01

    Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects. PMID:12814884

  4. Isotopic effect and amorphization of deuterated hydrogen hydrate under high pressure

    NASA Astrophysics Data System (ADS)

    Machida, Shin-Ichi; Hirai, Hisako; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

    2011-04-01

    High-pressure experiments of a mixture of H2 and D2O were performed using a diamond-anvil cell in the pressure range of 0.5-77.0 GPa under room temperature. Raman measurements revealed that an exchange of the hydrogen atoms occurred between fluid hydrogen and liquid water before the formation of deuterated hydrogen hydrate, and that a high-pressure structure of hydrogen hydrate, a filled ice Ic structure, formed at the same pressure as H2-H2O system hydrate. Additionally, the Raman spectra of the vibron for the D2, HD and H2 molecules revealed that the guest hydrogen molecules were partly extracted from the filled ice Ic structure above 20 GPa. The extraction of hydrogen molecules occurred depending on the atomic weight of the guest hydrogen molecules, and the heavier molecules were selectively released from the filled ice Ic structure. This isotopic effect in the extraction of hydrogen molecules showed differences in the stability of hydrogen hydrate depending on the species of guest molecules between D2, HD, and H2. Above 65 GPa, the filled ice Ic structure of hydrogen hydrate transformed to an amorphous phase. Formation of the amorphous phase showed the high-pressure limitation of hydrogen hydrate as a crystal structure and a new mechanism for the dissociation of gas hydrates under high pressure and room temperature.

  5. 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). PMID:24244971

  6. Hydrogen isotope measurements of organic acids and alcohols by Pyrolysis-GC-MS-TC-IRMS

    NASA Astrophysics Data System (ADS)

    Socki, R. A.; Fu, Q.; Niles, P. B.

    2011-12-01

    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 us and others as intermediary 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. Samples of carboxylic acid (C1 through C4) and alcohols (C1 through C4) were pyrolyzed at 200°C on a CDS Analytical. Inc. Model 5200° pyroprobe and passed through a Thermo Electron GC-MS-TC-IRMS system operating in continuous flow mode. The High Temperature Conversion step

  7. 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.

  8. Using equilibrium isotope effects to detect intramolecular OH/OH hydrogen bonds: structural and solvent effects.

    PubMed

    Vasquez, Thomas E; Bergset, Jon M; Fierman, Matthew B; Nelson, Alshakim; Roth, Joshua; Khan, Saeed I; O'Leary, Daniel J

    2002-03-27

    A comparative (1)H NMR study of partially deuterated 1,3- and 1,4-diols has demonstrated that intramolecular hydrogen bonds of different geometry can give rise to equilibrium isotope shifts of opposite sign in hydrogen-bond-accepting solvents such as DMSO-d(6), acetone-d(6), and THF-d(8). The sign inversion is interpreted in terms of the ability of solvent molecules to form competitive intermolecular hydrogen bonds with the diol and in terms of the limiting chemical shifts for the interior and exterior hydroxyl groups. Deuterium is shown to prefer the intermolecular solvent hydrogen bond by 10.9 +/- 0.5 cal/mol for 1,4-diol 3 dissolved in DMSO-d(6) at room temperature. Pyridine-d(5) is shown to be capable of amplifying positive (downfield) isotope shifts measured in DMSO-d(6), in some cases by as much as a factor of 3. Its use is demonstrated for the assignment of the syn or anti relative configuration of 2,4-pentanediol and for the amplification of isotope shifts used to detect intramolecular hydrogen bonds in alpha- and beta-cyclodextrin. Studies in apolar solvents such as CD(2)Cl(2) and benzene-d(6) reveal that the isotope shift is negative (upfield) for all hydrogen bond geometries studied. Larger isotope shifts are measured in benzene-d(6), and a rationale for this amplification is presented. The use of apolar solvents is particularly useful for assigning the syn or anti configuration of 2,4-pentanediol. PMID:11902884

  9. Calculating henry adsorption constants of molecular hydrogen at 77 K on alumophosphate zeolites with different microchannel sizes

    NASA Astrophysics Data System (ADS)

    Grenev, I. V.; Gavrilov, V. Yu.

    2014-01-01

    Adsorption isotherms of molecular hydrogen are measured at 77 K in a series of AlPO alumophosphate zeolites with different microchannel sizes. The potential of the intermolecular interaction of H2 is calculated within the model of a cylindrical channel of variable size. Henry constants are calculated for this model for arbitrary orientations of the adsorbate molecules in microchannels. The experimental and calculated values of the Henry adsorption constant of H2 are compared at 77 K on AlPO zeolites. The constants of intermolecular interaction are determined for the H2-AlPO system.

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

    PubMed

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

    2013-12-01

    Chloromethane (CH3 Cl) 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 (13) C of untransformed CH3 Cl 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

  11. 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.

  12. 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

  13. 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.

  14. Anion effects to deliver enhanced iridium catalysts for hydrogen isotope exchange processes.

    PubMed

    Kennedy, Alan R; Kerr, William J; Moir, Rory; Reid, Marc

    2014-10-28

    Synthesis of a series of iridium(I) complexes of the type [(COD)Ir(IMes)(PPh3)]X (X = BF4, OTf, and BArF) has been established. Application of these species in mild hydrogen isotope exchange processes revealed more efficient catalysis and, further, a wider solvent scope when employing larger, more weakly coordinating counterions. PMID:25208265

  15. Mineralogy and hydrogen isotope geochemistry of clay minerals in the Ohnuma geothermal area, Northeastern Japan

    NASA Astrophysics Data System (ADS)

    Marumo, Katsumi; Nagasawa, Keinosuke; Kuroda, Yoshimasu

    1980-04-01

    Mineralogical and hydrogen isotopic studies have been made on clay minerals occurring in the Ohnuma geothermal area, northeastern Japan. Here, clay minerals such as smectite, kaolinite, dickite, sericite, and chlorite were formed by hydrothermal alteration of Miocene rocks. A chemical equilibrium can be assumed to be attained from the fact that the amount of expandable layer in the interstratified chlorite/smectite decreases and the polytype of sericite changes from 1M to 2M 1 with increasing depth and temperature. The hydrogen isotopic composition (D/H) of the clay minerals is lighter than that of the geothermal and local meteoric waters by about 20-40‰. The hydrogen isotopic fractionation factors α mineral-water are as follows: 0.972-0.985 for kaolinite and dickite, 0.973-0.977 for sericite, and 0.954-0.987 for chlorite. In the temperature range from 100 to 250°C, the hydrogen isotopic fractionation factors between these minerals and water are not sensitive to the temperature. α chlorite-water depends on the kind of octahedrally coordinated cations which lie close to the hydroxyl groups; it becomes large with an increase of Mg content of chlorite.

  16. 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)

  17. 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

    2016-11-01

    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. PMID:27322904

  18. DFT model cluster studies of O₂ adsorption on hydrogenated titania sub-nanoparticles.

    PubMed

    Andreev, Alexey S; Kuznetsov, Vyacheslav N; Chizhov, Yuri V

    2013-11-01

    In the present paper, we examine the general applicability of different TiO2 model clusters to study of local chemical events on TiO2 sub-nanoparticles. Our previous DFT study of TiO2 activation through H adsorption and following deactivation by O2 adsorption using small amorphous Ti8O16 cluster were complemented by examination of rutile-type and spherical Ti15O30 nanoclusters. The obtained results were thoroughly compared with experimental data and results of related computational studies using other TiO2 models including periodic structures. It turned out that all considered model TiO2 model systems provide qualitatively similar results. It was shown that atomic hydrogen is adsorbed with negligible activation energy on surface O atoms, which is accompanied by the appearance of reduced Ti(3+) species and corresponding localized band gap 3d-Ti states. Oxygen molecule is adsorbed on Ti(3+) sites spontaneously forming molecular O2 (-) species by capturing an extra electron of Ti(3+) ion, which results in disappearance of Ti(3+) species and corresponding band gap states. Calculated g-tensor values of Ti(3+) and O2 (-) species agree well with the results of EPR studies and do not depend on the used TiO2 model cluster. Additionally, it was shown that the various cluster calculations provide results comparable with the calculations of periodic structures with respect to the modeling of chemical processes under study. As a whole, the present study approves the validity of molecular cluster approach to study of local chemical events on TiO2 sub-nanoparticles. PMID:24085538

  19. 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.

  20. Leaf water and plant wax hydrogen isotopes in a European sample network

    NASA Astrophysics Data System (ADS)

    Nelson, D. B.; Kahmen, A.

    2014-12-01

    The hydrogen isotopic composition of plant waxes in sediments is now routinely used as a hydroclimate proxy. This application is based largely on empirical calibrations that have demonstrated continental-scale correlations between source water and lipid hydrogen isotope values. But at smaller spatial scales and for individual locations it is increasingly recognized that factors that modify apparent fractionation between source water and leaf lipid hydrogen isotope values must also be considered. 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. Recent advances in theory have permitted mechanistic models to be developed that can be used to predict the mean leaf water hydrogen and oxygen 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. This will provide

  1. 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).

  2. Biogeochemistry of the Stable Isotopes of Hydrogen and Carbon in Salt Marsh Biota 1

    PubMed Central

    Smith, Bruce N.; Epstein, Samuel

    1970-01-01

    Deuterium to hydrogen ratios of 14 plant species from a salt marsh and lagoon were 55‰ depleted in deuterium relative to the environmental water. Carbon tetrachloride-extractable material from these plants was another 92‰ depleted in deuterium. This gave a fractionation factor from water to CCl4 extract of 1.147. This over-all fractionation was remarkably constant for all species analyzed. Plants also discriminate against 13C, particularly in the lipid fraction. Data suggest that different mechanisms for carbon fixation result in different fractionations of the carbon isotopes. Herbivore tissues reflected the isotopic ratios of plants ingested. Apparently different metabolic processes are responsible for the different degrees of fractionation observed for hydrogen and carbon isotopes. PMID:16657539

  3. Hydrogen isotope exchange in beryllium co-deposits: modelling and experiment

    NASA Astrophysics Data System (ADS)

    Kogut, D.; Douai, D.; Baldwin, M. J.; Doerner, R. P.; Sinelnikov, D.; Mamedov, N.; Kurnaev, V.; Becker, H. W.; Schwarz-Selinger, T.

    2016-02-01

    In order to understand the interaction mechanisms between hydrogenic species and beryllium co-deposits, a 1D Diffusion Trapping Model of Isotopic eXchange in Be (DITMIX) is developed. Hydrogen depth profiles from DITMIX are in good agreement with those measured by 15N-NRA on pre-characterised 600 nm thick Be:H layers (H/Be = 0.04), which were irradiated by D ions with a low flux of 1017 m-2 s-1 and an energy of 5 keV D-1, for different fluences and surface temperatures. Hence DITMIX provides a qualitative understanding of the isotope exchange mechanisms, although modelled versus measured D profiles show less agreement in the bulk, casting some doubt on the processes involved. For such low fluxes, DITMIX shows that the main factors determining isotopic exchange are the irradiation fluence and the surface temperature.

  4. 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. PMID:11879039

  5. 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

  6. Hydrogen isotope effect on storage behavior of U2Ti and UZr2.3

    NASA Astrophysics Data System (ADS)

    Jat, Ram Avtar; Sawant, S. G.; Rajan, M. B.; Dhanuskar, J. R.; Kaity, Santu; Parida, S. C.

    2013-11-01

    U2Ti and UZr2.3 alloys were prepared by arc melting method, vacuum annealed and characterized by XRD, SEM and EDX methods. Hydrogen isotope effect on the storage behavior of these alloys were studied by measuring the hydrogen/deuterium desorption pressure-composition-temperature (PCT) profiles in the temperature range of 573-678 K using a Sievert's type volumetric apparatus. It was observed that, in the temperature and pressure range of investigation, all the isotherms show a single desorption plateau. The PCT data reveals that both U2Ti and UZr2.3 alloys had normal isotope effects on hydrogen/deuterium desorption at all experimental temperatures. Thermodynamic parameters for dehydrogenation and dedeuteration reactions of the corresponding hydrides and deuterides of the above alloys were deduced from the PCT data.

  7. Catalyst for concentrating hydrogen isotopes and process for producing a support therefor

    SciTech Connect

    Isomura, S.; Kamijo, E.; Nakane, R.; Nishimoto, T.; Okita, K.

    1981-03-31

    A catalyst is claimed for concentrating hydrogen isotopes for use in performing hydrogen isotopes exchange between gaseous hydrogen and liquid water. The catalyst comprises a support of porous polytetrafluoroethylene having a total specific surface area of 2 to 80 m/sub 2//g as a result of mixing therewith 0.5 to 15% by weight of fluorocarbon or a porous styrene polymer or styrene/divinylbenzene copolymer having a specific surface area of at least 150 m/sub 2//g, and deposited on the support particles of at least one element selected from group VIII of the periodic table. A method for producing a support of porous polytetrafluoroethylene for such catalyst is also disclosed.

  8. 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)

  9. Stable-hydrogen isotope heterogeneity in keratinous materials: mass spectrometry and migratory wildlife tissue subsampling strategies.

    PubMed

    Wassenaar, Leonard I; Hobson, Keith A

    2006-01-01

    Stable-hydrogen isotope measurements (deltaD) of biological tissues have gained widespread acceptance in wildlife and forensic studies, especially in tracking geographical movements of birds and other species. Continuous-flow isotope-ratio mass spectrometry enables high-throughput deltaD analyses to be conducted on tissue samples as small as 0.15 mg, compared with conventional offline analyses that require 7-10 mg. This reduction in sample size has raised concerns regarding intra-sample hydrogen isotopic variance due to potential biological heterogeneities that could exceed interpretations of geospatial origin. To help resolve this, feathers were obtained from captive birds to examine isotopic variance expected due to sample size, location, and heterogeneity factors, and from selected wild birds to examine isotopic variance due to these and to additional dietary or location changes during feather growth. Captive bird feathers were sub-sampled along the vane on either side of a single feather at masses of 0.25, 0.35, 0.45, 0.6, 1.0 and 2.0 mg, and along the rachis. The results showed consistency of feather deltaD measurements across a wide range of sample masses. Within-feather deltaD isotopic variance for captive and some wild birds was as low as +/-3 per thousand for vane material, which corresponds to a geospatial resolution of about 1 degree of latitude in central North America. Intra-sample variance for the rachis was +/-5 per thousand, with lower deltaD values for both wild and captive birds. However, given the extraordinary intra-feather deltaD variance observed in some wild species, we recommend researchers first carefully assess the degree of intra- and inter-sample hydrogen isotopic variation in the selected tissue growth period for the species of interest before geospatial interpretations of origin are attempted. PMID:16862621

  10. 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.

  11. 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

  12. 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

  13. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1991-01-01

    The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in

  14. Germanium isotope fractionation during Ge adsorption on goethite and its coprecipitation with Fe oxy(hydr)oxides

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg S.; Galy, Albert; Schott, Jacques; Pokrovski, Gleb S.; Mantoura, Samia

    2014-04-01

    Isotopic fractionation of Ge was studied during Ge adsorption on goethite and its coprecipitation with amorphous Fe oxy(hydr)oxides. Regardless of the pH, surface concentration of adsorbed Ge or exposure time, the solution-solid enrichment factor for adsorption (Δ74/70Gesolution-solid) was 1.7 ± 0.1‰. The value of the Δ74Gesolution-solid in Fe-Ge coprecipitates having molar ratio 0.1 < (Ge/Fe)solid < 0.5 remained constant at 2.0 ± 0.4‰. For (Ge/Fe)solid ratio < 0.1, the Δ74Gesolution-solid increased with the decrease of Ge concentration in the solid phase, with the value as high as 4.4 ± 0.2‰ at (Ge/Fe)solid < 0.001, corresponding to the majority of natural settings. These results can be interpreted based on available structural data for adsorbed and coprecipitated Ge. It follows that Ge(OH)4° adsorption occurring as bidentate binuclear complexes at the goethite surface is characterised by an enrichment factor of ∼1.7‰, likely related to the distortion of the GeO4 tetrahedron and the formation of Ge-O-Fe bonds at the goethite surface as compared to aqueous solution. In contrast, coprecipitation yields more distorted edge-sharing GeO4 tetrahedra and, in the case of the most diluted samples, part of the Ge is found in coordination 6, replacing Fe(III) in octahedral positions. This produces a greater enrichment of the solid phase in lighter isotopes, mostly due to the increase in Ge-O bond distances and coordination number compared to aqueous solution, which is in line with the basic principles of isotope fractionation. Discharge of hydrothermal fluids, leading to massive Fe(OH)3 precipitation in the vicinity of the springs should, therefore, represent an isotopically-heavy source of dissolved Ge to the ocean. Similarly, groundwater discharge and Fe(OH)3 precipitation at the Earth’s surface, Fe oxy(hydr)oxide formation in soils and riverine organo-ferric colloids coagulation, leading to iron hydroxide precipitation in estuaries, should produce an

  15. 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

  16. Oxygen and hydrogen isotopes in thermal waters at Zunil, Guatemala

    SciTech Connect

    Fournier, R.O.; Hanshaw, B.B.; Urrutia Sole, J.F.

    1982-10-01

    Enthalpy-chloride relations suggest that a deep reservoir exists at Zunil with a temperature near 300/sup 0/C. Water from that reservoir moves to shallower and cooler local reservoirs, where it mixes with diluted water and then attains a new water-rock chemical equilibrium. This mixed water, in turn, generally is further diluted before being discharged from thermal springs. The stable-isotopic composition of the thermal water indicates that recharge for the deep water at Zunil comes mainly from local sources. The presence of measurable tritium, which suggests that the deep water has been underground about 20 to 30 years, also indicates a local source for the recharge.

  17. First-principles study of molecular hydrogen adsorption and dissociation on Al(n)Cr (n = 1-13) clusters.

    PubMed

    Guo, Ling

    2013-04-25

    Hydrogen adsorption dissociation on clusters is a widely studied subject that provides the opportunity to gain a basic understanding of the complicated nature of many interesting problems, such as hydrogen embrittlement of metals, catalytic processes, hydrogen storage, etc. In this study, I present density functional calculations of H2 adsorption and dissociation on small-sized Al(n)Cr clusters for n = 1-13. My results show that H2 is easily physically absorbed on the top Cr atom of AlnCr clusters with a side-on orientation rather than an end-on orientation. In addition, I investigate a possible dissociation mechanism and dissociation pathway of H2 on selected Al2Cr and Al7Cr. My findings suggest that the hydrogen dissociation behavior on Al(n)Cr clusters characterized by the activation barrier and reaction energy can be tuned by controllable doping. Thus, Al2Cr and Al7Cr clusters might serve as highly efficient and low-cost catalysts for hydrogen dissociation. PMID:23581518

  18. 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.

  19. A mechanistic model for interpretation of hydrogen and oxygen isotope ratios in tree-ring cellulose

    NASA Astrophysics Data System (ADS)

    Roden, John S.; Lin, Guanghui; Ehleringer, James R.

    2000-01-01

    A mechanistic model is presented to quantify both the physical and biochemical fractionation events associated with hydrogen and oxygen isotope ratios in tree-ring cellulose. The model predicts the isotope ratios of tree-rings, incorporating both humidity and source water environmental information. Components of the model include (1) hydrogen and oxygen isotope effects associated with leaf water enrichment; (2) incorporation of leaf water isotope ratio values into photosynthetic carbohydrates along with the biochemical fractionation associated with autotrophic synthesis; (3) transport of exported carbohydrates (such as sucrose) from leaves to developing xylem in shoots and stems where cellulose is formed; (4) a partial exchange of oxygen and hydrogen isotopes in carbohydrates with xylem sap water during conversion into cellulose; and (5) a biochemical fractionation associated with cellulose synthesis. A modified version of the Craig-Gordon model for evaporative enrichment adequately described leaf water δD and δ 18O values. The leaf water model was robust over a wide range of leaf waters for both controlled experiments and field studies, far exceeding the range of values to be expected under natural conditions. The isotopic composition of cellulose was modeled using heterotrophic and autotrophic fractionation factors from the literature as well as the experimentally derived proportions of H and O that undergo exchange with xylem water during cellulose synthesis in xylem cells of tree-rings. The fraction of H and O from carbohydrates that exchange with xylem sap water was estimated to be 0.36 and 0.42, respectively. The proportions were based on controlled, long-term greenhouse experiments and field studies where the variations in the δD and δ 18O of tree-ring cellulose were measured under different source water isotopic compositions. The model prediction that tree-ring cellulose contains information on environmental water source and atmospheric vapor pressure

  20. Si isotopic structure of the infrared absorption of the fully hydrogenated vacancy in silicon.

    PubMed

    Clerjaud, B; Pajot, B

    2013-05-14

    An infrared absorption spectrum consisting in three lines observed around 2223 cm(-1) at liquid helium temperature characterizes a defect common in silicon crystals containing hydrogen. Several investigations of this spectrum have converged towards its assignment to a fully hydrogenated lattice vacancy defect V(Si-H)4. However, the fact that the ratios of the intensities of the three lines have been reported to be proportional to the natural abundances of the three silicon isotopes suggests that only one Si atom is involved in the defect, apparently contradicting the above assignment. In this paper, the spectroscopic investigation of this defect is revisited and the Si-related isotopic structures of V(Si-H)4 and V(Si-D)4 defects are modeled. It is shown that the near proportionalities observed between the intensities of these lines and the abundances of the Si isotopes are fortuitous. Our analysis of the isotope dependence of the 2223 cm(-1) line finds the V(Si-H)4 model to be correct and that the model of a single interstitial Si atom complexed with H can be rejected. The investigation is extended to the analysis of tetra-hydrogenated vacancy trapped by a carbon atom. PMID:23676054

  1. Spectroscopy of Superheavy Hydrogen Isotopes in Stopped-Pion Absorption by Nuclei

    SciTech Connect

    Gurov, Yu.B.; Aleshkin, D.V.; Behr, M.N.; Lapushkin, S.V.; Morokhov, P.V.; Pechkurov, V.A.; Poroshin, N.O.; Sandukovsky, V.G.; Tel'kushev, M.V.; Chernyshev, B.A.; Tschurenkova, T.D.

    2005-03-01

    The structure of levels of superheavy hydrogen isotopes {sup 4-6}H is analyzed on the basis of a record statistics of experimental data on the absorption of negatively charged pions by light nuclei. Qualitatively new experimental data are obtained for the spectroscopy of the superheavy hydrogen isotopes {sup 5}H and {sup 6}H. Peaks due to four resonance states of {sup 5}H are observed in the missing-mass spectra for the reaction channels {sup 9}Be({pi}{sup -}, pt)X and {sup 9}Be({pi}{sup -}, dd)X. A structure that is associated with four resonance states of {sup 6}H is observed in the missing-mass spectra for the reaction channels {sup 9}Be({pi}{sup -}, pd)X and {sup 11}B({pi}{sup -}, p{sup 4}He)X. On the basis of the results presented for ground-state parameters, it can be concluded that the binding energy of superheavy hydrogen isotopes decreases as the number of neutrons increases. Excited levels of the isotopes {sup 5}H and {sup 6}H are observed for the first time. On the energy scale, all of these states lie above the threshold for decay to free nucleons.

  2. Si isotopic structure of the infrared absorption of the fully hydrogenated vacancy in silicon

    NASA Astrophysics Data System (ADS)

    Clerjaud, B.; Pajot, B.

    2013-05-01

    An infrared absorption spectrum consisting in three lines observed around 2223 cm-1 at liquid helium temperature characterizes a defect common in silicon crystals containing hydrogen. Several investigations of this spectrum have converged towards its assignment to a fully hydrogenated lattice vacancy defect V(Si-H)4. However, the fact that the ratios of the intensities of the three lines have been reported to be proportional to the natural abundances of the three silicon isotopes suggests that only one Si atom is involved in the defect, apparently contradicting the above assignment. In this paper, the spectroscopic investigation of this defect is revisited and the Si-related isotopic structures of V(Si-H)4 and V(Si-D)4 defects are modeled. It is shown that the near proportionalities observed between the intensities of these lines and the abundances of the Si isotopes are fortuitous. Our analysis of the isotope dependence of the 2223 cm-1 line finds the V(Si-H)4 model to be correct and that the model of a single interstitial Si atom complexed with H can be rejected. The investigation is extended to the analysis of tetra-hydrogenated vacancy trapped by a carbon atom.

  3. First-Principles Study of Electronic Structure and Hydrogen Adsorption of 3d Transition Metal Exposed Paddle Wheel Frameworks

    SciTech Connect

    Bak, J. H.; Le, V. D.; Kang, J.; Wei, S. H.; Kim, Y. H.

    2012-04-05

    Open-site paddle wheels, comprised of two transition metals bridged with four carboxylate ions, have been widely used for constructing metal-organic frameworks with large surface area and high binding energy sites. Using first-principles density functional theory calculations, we have investigated atomic and electronic structures of various 3d transition metal paddle wheels before and after metal exposure and their hydrogen adsorption properties at open metal sites. Notably, the hydrogen adsorption is impeded by covalent metal-metal bonds in early transition metal paddle wheels from Sc to Cr and by the strong ferromagnetic coupling of diatomic Mn and Fe in the paddle wheel configurations. A significantly enhanced H{sub 2} adsorption is predicted in the nonmagnetic Co{sub 2} and Zn{sub 2} paddle wheel with the binding energy of {approx}0.2 eV per H{sub 2}. We also propose the use of two-dimensional Co{sub 2} and Zn{sub 2} paddle wheel frameworks that could have strongly adsorbed dihydrogen up to 1.35 wt % for noncryogenic hydrogen storage applications.

  4. 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. PMID:16977462

  5. Measuring and utilizing the hydrogen isotopic composition of deep-sea corals

    NASA Astrophysics Data System (ADS)

    Davin, Samuel; Hillaire-Marcel, Claude; Edinger, Evan; Gelinas, Yves

    2016-04-01

    Despite the widespread use of hydrogen isotopic analysis of bioarchives in paleoenvironmental reconstructions, no previously-published work has yet attempted to measure or utilize the hydrogen isotopic composition (δD) of deep-sea corals. Geographically ubiquitous and with lifespans on the scale of hundreds of years, δD measurements of deep-sea corals have the potential to elucidate physical paleoceanographic parameters at well-resolved spatial and temporal resolutions. We present a method for the determination of annually-resolved δD from deep-sea corals measured from gorgonin, a complex proteinaceous material making up the horny skeleton of gorgonian corals. We address the issue of exchangeable hydrogen in gorgonin by controlling the isotopic composition of exchangeable hydrogen using a heated batch dual-equilibration technique. Coupled with δ15N measurements, we attempt to identify the relationships between trophic feeding levels, physical oceanographic parameters, and the δD of gorgonin from corals collected from chemically distinct ocean basins. Preliminary results from 43 samples indicate reproducible measurements on coral species Primnoa pacifica, Primnoa resedaeformis, and Keratoisis grayii with bulk δD values ranging from -40‰ to -110‰ and bulk δ15N values ranging from +13‰ to +17‰. Final results will include a full suite of non-exchangeable δD values and δ15N of corals from the Labrador Sea and from the Gulf of Alaska.

  6. Adsorption of charged and neutral polymer chains on silica surfaces: The role of electrostatics, volume exclusion, and hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Spruijt, Evan; Biesheuvel, P. M.; de Vos, Wiebe M.

    2015-01-01

    We develop an off-lattice (continuum) model to describe the adsorption of neutral polymer chains and polyelectrolytes to surfaces. Our continuum description allows taking excluded volume interactions between polymer chains and ions directly into account. To implement those interactions, we use a modified hard-sphere equation of state, adapted for mixtures of connected beads. Our model is applicable to neutral, charged, and ionizable surfaces and polymer chains alike and accounts for polarizability effects of the adsorbed layer and chemical interactions between polymer chains and the surface. We compare our model predictions to data of a classical system for polymer adsorption: neutral poly(N -vinylpyrrolidone) (PVP) on silica surfaces. The model shows that PVP adsorption on silica is driven by surface hydrogen bonding with an effective maximum binding energy of about 1.3 kBT per PVP segment at low p H . As the p H increases, the Si-OH groups become increasingly dissociated, leading to a lower capacity for H bonding and simultaneous counterion accumulation and volume exclusion close to the surface. Together these effects result in a characteristic adsorption isotherm, with the adsorbed amount dropping sharply at a critical p H . Using this model for adsorption data on silica surfaces cleaned by either a piranha solution or an O2 plasma, we find that the former have a significantly higher density of silanol groups.

  7. Monte Carlo Simulations Probing the Adsorptive Separation of Hydrogen Sulfide/Methane Mixtures Using All-Silica Zeolites.

    PubMed

    Shah, Mansi S; Tsapatsis, Michael; Siepmann, J Ilja

    2015-11-10

    Selective removal of hydrogen sulfide (H2S) from sour natural gas mixtures is one of the key challenges facing the natural gas industry. Adsorption and pervaporation processes utilizing nanoporous materials, such as zeolites, can be alternatives to highly energy-intensive amine-based absorption processes. In this work, the adsorption behavior of binary mixtures containing H2S and methane (CH4) in seven different all-silica zeolite frameworks (CHA, DDR, FER, IFR, MFI, MOR, and MWW) is investigated using Gibbs ensemble Monte Carlo simulations at two temperatures (298 and 343 K) and pressures ranging from 1 to 50 bar. The simulations demonstrate high selectivities that, with the exception of MOR, increase with increasing H2S concentration due to favorable sorbate-sorbate interactions. The simulations indicate significant inaccuracies of predictions using unary adsorption data and ideal adsorbed solution theory. In addition, the adsorption of binary H2S/H2O mixtures in MFI is considered to probe whether the presence of H2S induces coadsorption and reduces the hydrophobic character of all-silica zeolites. The simulations show preferential adsorption of H2S from moist gases with a selectivity of about 18 over H2O. PMID:26473306

  8. 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

  9. 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.

  10. Predicting the Hydrogen Isotope Ratios of Leaf Waxes Across Landscapes

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Berke, M. A.; Hambach, B.; Ehleringer, J. R.

    2014-12-01

    Leaf wax n-alkanes 2H/1H ratios are widely used as a proxy of paleoprecipitation in climate reconstruction. While the broad nature of the relationships between n-alkane δ2H values and climate are appreciated on geologic scales, the quantitative details of what this proxy is reflecting remain ambiguous on plant and ecosystem levels. Areas of uncertainty on these smaller scales of importance to geologic interpretations are both the biosynthetic fractionation and the leaf-growth interval that is recorded by the isotope signal. To clarify these details, we designed a series of experiments in which modern plants were grown under controlled and monitored conditions. To determine the biosynthetic fractionation, we analyzed n-alkanes from plant grown hydroponically on isotopically distinct waters and under contrasting and controlled humidities. We observed δ2H values of n-alkane were linearly related to growth water δ2H values, but with slope differences associated with humidity. These findings suggested leaf water were central controls on δ2H values of n-alkane and support a relatively constant biosynthetic fractionation factor between leaf water and n-alkanes. To determine the interval that the leaf wax isotope signal reflects, we studied a species naturally growing on water with a constant δ2H value. Here we found the δ2H values of n-alkanes recorded only a two-week period during leaf flush and did not vary thereafter. These data indicated the δ2H values of n-alkanes record conditions early in the season, rather than integrating over the entire growing season. Using these data, we are beginning to develop geospatial predictions of the δ2H values of n-alkane across landscapes for given climate conditions, plant phenologies, and ecosystems. These emerging modeling tools may be used to assess modern ecosystem dynamics, to estimate weathering of leaf waxes to geologic repositories, and to define and test paleoclimate reconstructions from the δ2H values of n-alkanes.

  11. 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.

  12. Hydrogen Isotopes in Eocene River Gravels and Paleoelevation of the Sierra Nevada

    NASA Astrophysics Data System (ADS)

    Mulch, Andreas; Graham, Stephan A.; Chamberlain, C. Page

    2006-07-01

    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.

  13. Hydrogen isotopes in Eocene river gravels and paleoelevation of the Sierra Nevada.

    PubMed

    Mulch, Andreas; Graham, Stephan A; Chamberlain, C Page

    2006-07-01

    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. PMID:16825568

  14. Hydrogen isotope transfer in austenitic steels and high-nickel alloy during in-core irradiation

    SciTech Connect

    Polosukhin, B.G.; Sulimov, E.M.; Zyrianov, A.P.; Kalinin, G.M.

    1995-10-01

    The transfer of protium and deuterium in austenitic chromium-nickel steels and in a high-nickel alloy was studied in a specially designed facility. The transfer parameters of protium and deuterium were found to change greatly during in-core irradiation, and the effects of irradiation increased as the temperature decreased. Thus, at temperature T<673K, the relative increase in the permeability of hydrogen isotopes under irradiation can be orders of magnitude higher in these steels. Other radiation effects were also observed, in addition to the changes from the initial values in the effects of protium and deuterium isotopic transfer. 4 refs., 3 figs., 2 tabs.

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  18. 3d-transition metal induced enhancement of molecular hydrogen adsorption on Mg(0001) surface: An Ab-initio study

    NASA Astrophysics Data System (ADS)

    Banerjee, Paramita; Das, G. P.

    2016-05-01

    In our effort to do first principles design of suitable materials for hydrogen storage, we have explored the interaction characteristics of a hydrogen molecule with pure as well as a 3d-transition metal (TM) atom doped Mg(0001) surface using density functional theory (DFT) based approach. Doping of a 3d-TM atom by creating a vacancy on the top most layer of Mg(0001) surface, enhances the molecular hydrogen adsorption efficiency of this surface by ~ 6 times. The TM atom gains some charge from the defected site of the Mg(0001) surface, becomes anionic and adsorbs the hydrogen molecule via Anti Kubas-type interaction. The interaction energy of this H2 molecule, including van der Waals dispersion correction, turns out to be ~ 0.4 eV, which falls in the right energy window between physisorption and chemisorption. On full coverage of this 3d-TM atom doped Mg(0001) surface with hydrogen molecules, the gravimetric density of hydrogen has been estimated to be ~ 5.6 wt %, thereby satisfying the criteria set by the department of energy (DOE) for efficient hydrogen storage.

  19. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1994-01-01

    The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.

  20. 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.

  1. 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).

  2. Analysis of hydrogen adsorption and surface binding configuration on tungsten using direct recoil spectrometry

    SciTech Connect

    Kolasinski, R. D.; Hammond, K. D.; Whaley, J. A.; Buchenauer, D. A.; Wirth, B. D.

    2014-12-03

    In our work, we apply low energy ion beam analysis to examine directly how the adsorbed hydrogen concentration and binding configuration on W(1 0 0) depend on temperature. We exposed the tungsten surface to fluxes of both atomic and molecular H and D. We then probed the H isotopes adsorbed along different crystal directions using 1–2 keV Ne+ ions. At saturation coverage, H occupies two-fold bridge sites on W(1 0 0) at 25 °C. Moreover, the H coverage dramatically changes the behavior of channeled ions, as does reconstruction of the surface W atoms. For the exposure conditions examined here, we find that surface sites remain populated with H until the surface temperature reaches 200 °C. Then, we observe H rapidly desorbing until only a residual concentration remains at 450 °C. Development of an efficient atomistic model that accurately reproduces the experimental ion energy spectra and azimuthal variation of recoiled H is underway.

  3. Analysis of hydrogen adsorption and surface binding configuration on tungsten using direct recoil spectrometry

    DOE PAGESBeta

    Kolasinski, R. D.; Hammond, K. D.; Whaley, J. A.; Buchenauer, D. A.; Wirth, B. D.

    2014-12-03

    In our work, we apply low energy ion beam analysis to examine directly how the adsorbed hydrogen concentration and binding configuration on W(1 0 0) depend on temperature. We exposed the tungsten surface to fluxes of both atomic and molecular H and D. We then probed the H isotopes adsorbed along different crystal directions using 1–2 keV Ne+ ions. At saturation coverage, H occupies two-fold bridge sites on W(1 0 0) at 25 °C. Moreover, the H coverage dramatically changes the behavior of channeled ions, as does reconstruction of the surface W atoms. For the exposure conditions examined here, wemore » find that surface sites remain populated with H until the surface temperature reaches 200 °C. Then, we observe H rapidly desorbing until only a residual concentration remains at 450 °C. Development of an efficient atomistic model that accurately reproduces the experimental ion energy spectra and azimuthal variation of recoiled H is underway.« less

  4. Hydrogen Isotope Separation Factor Measurement for Single Stage Hydrogen Separators and Parameters for a Large-Scale Separation System

    SciTech Connect

    Luo, D.L.; Xiong, Y.F.; Song, J.F.; Huang, G.Q.

    2005-07-15

    A Concept design for large-scale hydrogen ISS based on a single Pd alloy membrane separator cascade has been presented. Separators to investigate the feasibility of the Pd membrane separator cascade concept have been designed and the separation performance of the separators is given. Results show that the separation factors, which are between 1.4 and 1.8 at the operation temperature, are large enough for a practical separation system design. Estimation results indicate that a 2.0m{sup 2} Pd membrane is needed for a 20mol/h and 12 stages batch ISS, and an approximately 50m{sup 2} Pd membrane is needed for a 200mol/h and 26 stages ISS. It is clear that the separator cascade concept is both reasonable and practicable for large-scale hydrogen isotope separation.

  5. 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.

  6. Measuring terrestrial subsidies to aquatic food webs using stable isotopes of hydrogen.

    PubMed

    Doucett, Richard R; Marks, Jane C; Blinn, Dean W; Caron, Melanie; Hungate, Bruce A

    2007-06-01

    Understanding river food webs requires distinguishing energy derived from primary production in the river itself (autochthonous) from that produced externally (allochthonous), yet there are no universally applicable and reliable techniques for doing so. We compared the natural abundance stable isotope ratios of hydrogen (deltaD) of allochthonous and autochthonous energy sources in four different aquatic ecosystems. We found that autochthonous organic matter is uniformly far more depleted in deuterium (lower deltaD values) than allochthonous: an average difference of approximately 100% per hundred. We also found that organisms at higher trophic levels, including both aquatic invertebrates and fish, have deltaD values intermediate between aquatic algae and terrestrial plants. The consistent differences between leaves and algae in deltaD among these four watersheds, along with the intermediate values in higher trophic levels, indicate that natural abundance hydrogen isotope signatures are a powerful tool for partitioning energy flow in aquatic ecosystems. PMID:17601150

  7. 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.

  8. Hydrogen isotope evidence for the origin and evolution of the carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Eiler, John M.; Kitchen, Nami

    2004-03-01

    We present new hydrogen isotope data for separated matrix, hydrated chondrules, and other hydrated coarse silicate fragments from nine carbonaceous chondrites. These data were generated using a micro-analytical method involving stepped combustion of tens to hundreds of micrograms of hydrous solids. We also re-evaluate hydrogen isotope data from previous conventional stepped combustion experiments on these and other carbonaceous chondrites. Hydrogen isotope compositions of matrix and whole-rock samples of CM chondrites are correlated with oxygen isotope indices, major and minor-element abundances, and abundance and isotope ratios of other highly volatile elements. These correlations include a monotonic decrease in δD with increasing extent of aqueous alteration and decreasing abundances of highly volatile elements (including C, N and Ar), between extremes of ˜0‰ (least altered, most volatile rich) and -200‰ (most altered, least volatile rich). In plots involving only abundances and/or isotope ratios of highly volatile elements, CI chondrites fall on the high-δD, volatile rich end of the trends defined by CM chondrites; i.e., CI chondrites resemble the least altered CM chondrites in these respects. These trends suggest the protoliths of the CM chondrites (i.e., before aqueous alteration) contained an assemblage of volatiles having many things in common with those in the CI chondrites. If so, then the volatile-element inventory of the CI chondrites was a more widespread component of early solar system objects than suggested by the scarcity of recognized CI meteorites. Differences in volatile-element chemistry between the CI and average CM chondrites can be attributed to aqueous alteration of the latter. Previous models of carbonaceous chondrite aqueous alteration have suggested: (1) the protoliths of the CM chondrites are volatile poor objects like the CO or CV chondrites; and (2) the CI chondrites are more altered products of the same process producing the CM

  9. 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)

  10. Stable hydrogen-isotope analysis of methyl chloride emitted from heated halophytic plants

    NASA Astrophysics Data System (ADS)

    Greule, Markus; Huber, Stefan G.; Keppler, Frank

    2012-12-01

    Stable isotope techniques are increasingly applied to study atmospheric budgets of methyl halides. Here we use compound specific thermal conversion isotope ratio mass spectrometry to measure the stable hydrogen isotope values of methyl chloride (δHCl) released thermally from dried leaves of halophyte plants collected from different geographical locations. We developed an automated purification and pre-concentration unit to enable measurement of δHCl from samples (100 ml) when mixing ratios were as low as 1 ppmv. Even though this is considerably higher than normal atmospheric mixing ratios this unit enabled measurement of the δ2H values of CH3Cl released during heating of samples at temperatures ranging from 30 to 300 °C. No substantial changes of δHCl values were observed over this temperature range. However, the δHCl values of all plants examined were strongly depleted (-178 ± 34‰) relative to the δ2H values of their modelled meteoric water, but differ only by 1-50‰ from those observed for their methoxyl groups. Our results indicate that plant methoxyl groups are an important precursor of the methyl group for CH3Cl thermally emitted from lyophilised and homogenized dry halophyte leaves. Furthermore, the thermal reaction producing CH3Cl did not show a substantial kinetic hydrogen isotope fractionation between CH3Cl and precursor methoxyl groups over the temperature range investigated. Moreover, we found a moderate linear correlation (R2 = 0.37) for the relationship between δHCl values released from halophytes and the δ2H values of modelled precipitation at their geographical locations. As CH3Cl emissions from terrestrial vegetation, including senescent and dry plants and biomass burning, are considered to provide a substantial fraction of the global emissions our findings are important when establishing a global hydrogen isotope model for atmospheric CH3Cl.

  11. Enantioselective hydrogenation. IV. Hydrogen isotope exchange in 10,11-dihydrocinchonidine and in quinoline catalyzed by platinum group metals

    SciTech Connect

    Bond, G.; Wells, P.B.

    1994-12-01

    Hydrogen isotope (H/D) exchange in the alkaloid 10,11-dihydrocinchonidine has been studied over 6.4% Pt/silica (EUROPT-1), 5% Ru/alumina, 5% Rh/alumina, and 5% Pd/alumina at 293 K using C{sub 2}H{sub 5}OD and D{sub 2} as solvent and deuterium source. Exchange was accompanied by hydrogenation. Over Pt, fast exchange occurred in the hydroxyl group followed by multiple exchange in which alkaloid molecules containing, 2, 3, 4 and 5 deuterium atoms were formed simultaneously. Mass spectrometry and {sup 1}H NMR showed that this multiple exchange occurred in the quinoline ring system and at C{sub 9}, but not in the quinuclidine ring system. The pattern of exchange in Ru was similar. Over Rh extensive hydrogenolysis of the quinuclidine ring system occurred, and over Pd the quinoline ring system was rapidly hydrogenated. Quinoline exchange and hydrogenation were also studied at 293 K; relatively rapid exchange occurred over Pt, Ru, and Rh, particularly at the 2- and 8-positions, whereas hydrogenation without significant exchange occurred over Pd. 10,11-Dihydrocinchonidine is adsorbed on Pt and Ru via the quinoline ring system and the multiple nature of the exchange indicates that the quinoline moiety is adsorbed approximately parallel to the metal surface by multicenter {pi}-bonding. An additional interaction of the alkaloid molecule with the surface occurs at carbon atom C{sub 9}, which may interpret the slower exchange in the alkaloid by comparison with that in quinoline. This study supports and enhances the model proposed to interpret the origin of enantioselectivity in pyruvate hydrogenation over Pt and Ir modified by cinchona alkaloids. The similarities of exchange over Pt and Ru suggest that enantioselective catalysis should be achievable over Ru. 28 refs., 2 figs., 2 tabs.

  12. 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.

  13. 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

  14. 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.

  15. Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption

    NASA Astrophysics Data System (ADS)

    Höhener, Patrick; Yu, Xianjing

    2012-03-01

    Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from - 0.13 ± 0.04‰ (benzene) to - 0.52 ± 0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between - 2.4 and - 9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from - 19 ± 5.4‰ (benzene) to - 64 ± 30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for 13C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants.

  16. 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)

  17. Adsorption and Desorption of Hydrogen by Gas-Phase Palladium Clusters Revealed by In Situ Thermal Desorption Spectroscopy.

    PubMed

    Takenouchi, Masato; Kudoh, Satoshi; Miyajima, Ken; Mafuné, Fumitaka

    2015-07-01

    Adsorption and desorption of hydrogen by gas-phase Pd clusters, Pdn(+), were investigated by thermal desorption spectroscopy (TDS) experiments and density functional theory (DFT) calculations. The desorption processes were examined by heating the clusters that had adsorbed hydrogen at room temperature. The clusters remaining after heating were monitored by mass spectrometry as a function of temperature up to 1000 K, and the temperature-programmed desorption (TPD) curve was obtained for each Pdn(+). It was found that hydrogen molecules were released from the clusters into the gas phase with increasing temperature until bare Pdn(+) was formed. The threshold energy for desorption, estimated from the TPD curve, was compared to the desorption energy calculated by using DFT, indicating that smaller Pdn(+) clusters (n ≤ 6) tended to have weakly adsorbed hydrogen molecules, whereas larger Pdn(+) clusters (n ≥ 7) had dissociatively adsorbed hydrogen atoms on the surface. Highly likely, the nonmetallic nature of the small Pd clusters prevents hydrogen molecule from adsorbing dissociatively on the surface. PMID:26043808

  18. Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

    PubMed

    Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

    2012-06-27

    Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions. PMID:22667349

  19. Adsorption of Water Monomer and Clusters on Platinum(111) Terrace and Related Steps and Kinks I. Configurations, Energies, and Hydrogen Bonding

    SciTech Connect

    Arnadottir, Liney; Stuve, Eric M.; Jonsson, Hannes

    2010-10-01

    Adsorption and rotation of water monomer, dimer, and trimer on the (111) terrace, (221) and (322) stepped, and (763) and (854) kinked surfaces of platinum were studied by density functional theory calculations using the PW91 approximation to the energy functional. On the (111) terrace, water monomer and the donor molecule of the dimer and trimer adsorb at atop sites. The permolecule adsorption energies of the monomer, dimer, and trimer are 0.30, 0.45, and 0.48 eV, respectively. Rotation of monomers, dimers, and trimers on the terrace is facile with energy barriers of 0.02 eV or less. Adsorption on steps and kinks is stronger than on the terrace, as evidenced by monomer adsorption energies of 0.46 to 0.55 eV. On the (221) stepped surface the zigzag extended configuration is most stable with a per-molecule adsorption energy of 0.57 eV. On the (322) stepped surface the dimer, two configurations of the trimer, and the zigzag configuration have similar adsorption energies of 0.55 ± 0.02 eV. Hydrogen bonding is strongest in the dimer and trimer adsorbed on the terrace, with respective energies of 0.30 and 0.27 eV, and accounts for their increased adsorption energies relative to the monomer. Hydrogen bonding is weak to moderate for adsorption at steps, with energies of 0.04 to 0.15 eV, as the much stronger water-metal interactions inhibit adsorption geometries favorable to hydrogen bonding. Correlations of hydrogen bond angles and energies with hydrogen bond lengths are presented. On the basis of these DFT/PW91 results, a model for water cluster formation on the Pt(111) surface can be formulated where kink sites nucleate chains along the top of step edges, consistent with the experimental findings of Morgenstern et al., Phys. Rev. Lett., 77 (1996) 703.

  20. Thermodynamic properties of hydrogen-water adsorption at terraces and steps of Pt(111) vicinal surface electrodes

    NASA Astrophysics Data System (ADS)

    Gómez-Marín, Ana M.; Feliu, Juan M.

    2016-04-01

    In this work, the effect of temperature on the adsorption states of Pt(111) vicinal surface electrodes in perchloric acid is studied through a thermodynamic analysis. The method allows calculating thermodynamic properties of the interface. In this framework, the concept of the generalized isotherm and the statistical thermodynamics description are applied to calculate formal entropies, enthalpies and Gibbs energies, ΔGbari0, of the adsorption processes at two-dimensional terraces and one-dimensional steps. These values are compared with data from literature. Additionally, the effect of the step density on ΔGbari0 and on the lateral interactions between adsorbed species, ωij, at terraces and steps is also determined. Calculated ΔGbari0, entropies and enthalpies are almost temperature-independent, especially at steps, but they depend on the step orientation. In contrast, ΔGbari0 and ωij at terraces depend on the step density, following a linear tendency for terrace lengths larger than 5 atoms. However, while ΔGbari0 increases with the step density, ωij decreases. Results were explained by considering the modification in the energetic surface balance by hydrogen, Hads, and water, H2Oads, co-adsorption on the electrode, which in turn determines the whole adsorption processes on terraces and steps.

  1. Grasping hydrogen adsorption and dynamics in metal-organic frameworks using (2)H solid-state NMR.

    PubMed

    Lucier, Bryan E G; Zhang, Yue; Lee, Kelly J; Lu, Yuanjun; Huang, Yining

    2016-06-18

    Record greenhouse gas emissions have spurred the search for clean energy sources such as hydrogen (H2) fuel cells. Metal-organic frameworks (MOFs) are promising H2 adsorption and storage media, but knowledge of H2 dynamics and adsorption strengths in these materials is lacking. Variable-temperature (VT) (2)H solid-state NMR (SSNMR) experiments targeting (2)H2 gas (i.e., D2) shed light on D2 adsorption and dynamics within six representative MOFs: UiO-66, M-MOF-74 (M = Zn, Mg, Ni), and α-M3(COOH)6 (M = Mg, Zn). D2 binding is relatively strong in Mg-MOF-74, Ni-MOF-74, α-Mg3(COOH)6, and α-Zn3(COOH)6, giving rise to broad (2)H SSNMR powder patterns. In contrast, D2 adsorption is weaker in UiO-66 and Zn-MOF-74, as evidenced by the narrow (2)H resonances that correspond to rapid reorientation of the D2 molecules. Employing (2)H SSNMR experiments in this fashion holds great promise for the correlation of MOF structural features and functional groups/metal centers to H2 dynamics and host-guest interactions. PMID:27181834

  2. Adsorption and diffusion of hydrogen on Pd(211) and Pd(111): Results from first-principles electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Hong, Sampyo; Rahman, Talat S.

    2007-04-01

    We have carried out first-principles calculations of H adsorption on Pd(211) using density-functional theory with the generalized gradient approximation in the plane-wave basis to find out that the most preferred is the threefold hollow site on the terrace of Pd(211) with an adsorption energy of 0.52eV : the hcp and fcc sites being almost energetically equally favorable. For subsurface H adsorption on Pd(211), the octahedral site with an adsorption energy of 0.19eV is slightly more favorable than the tetrahedral site (0.18eV) . Our calculated activation energy barrier for H to diffuse from the preferred surface site to the subsurface one on Pd(211) is 0.33eV , as compared with 0.41eV on Pd(111). Thus, there is an enhancement of the probability of finding subsurface hydrogen in Pd(211). Additionally, we find the diffusion barriers for H on the terraces of Pd(211) to be 0.11eV , while that along the step edge to be only 0.05eV and that within the second layer (subsurface) to be 0.15eV .

  3. Hydrogen adsorption induced antiferrodistortive distortion and metallization at the (001) surface of SrTiO{sub 3}

    SciTech Connect

    Yang, Yi; Lin, Chen-Sheng; Cheng, Wen-Dan

    2015-09-14

    SrTiO{sub 3} (STO) is attracting lots of research interests due to the rich physics and properties presented at its surfaces and the interfaces of STO with other transition metal oxides. Based on density functional theory methods, we have investigated the influence of hydrogen (H) atoms adsorption at the (001) surface of STO on the geometrical and electronic structures of the surface. We find that H adsorption induces significant antiferrodistortive (AFD) distortion of TiO{sub 6} octahedra at the surface. By calculating H adsorption energy, we show that AFD distortion makes a significant contribution to the stability of H adsorbed STO surfaces. The calculated energy position of O-H bond states by hybrid functional method is 9.9 eV below Fermi level, in agreement with experimental value of 10 eV. The electrons donated by H atoms first occupy several d{sub xy} bands and then start to fill in degenerate d{sub yz}/d{sub xz} bands, indicating the metallization of initially insulating STO. The band splitting and occupy sequence calculated here are consistent with recent angle-resolved photoemission spectroscopy experiments. Our results reveal that H adsorption changes the atomic and electronic structures and thus induce fascinating properties at the surface of STO.

  4. Isotopic Separation Analysis of Infinitesimal Concentrations of Hydrogen Using Trace Reduction Detector

    SciTech Connect

    Kawano, Takao; Tsuboi, Naohiro; Tsujii, Hirotsugu; Asakura, Yamato; Uda, Tatsuhiko

    2005-07-15

    A previously developed analyzer for detecting extremely small concentrations of hydrogen in air was evaluated by using it to distinguish hydrogen isotopes. The analyzer utilizes the functions of a gas chromatograph and an atomic absorption spectrophotometer and is based on the reduction reaction of mercuric oxide with hydrogen. Three test samples were used: gas mixtures containing both protium and deuterium with almost equal concentrations of about 5, 20, or 50 cm{sup 3}/1000 m{sup 3} diluted in nitrogen. Each measurement was repeated more than 30 times, and chromatograms were obtained for each test sample. Examination of the chromatograms showed that the retention times for the protium and deuterium could be clearly distinguished. The retention times were virtually constant and indistinguishable, independent of the concentration and repetition time. The peak areas for the protium and deuterium were also stable, independent of the repetition time. Moreover, there was a clear linear relationship between the peak areas and concentrations for both elements. These results show that the analyzer can distinguish the two hydrogen isotopes and estimate concentrations of each as small as about 5 cm{sup 3}/1000 m{sup 3}. They also show that it may be possible to use the analyzer to monitor tritium concentrations.

  5. 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

  6. 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.

  7. Seasonal Water Usage by Juniperus Ashei: Assessment With Stable Isotopes of Hydrogen and Oxygen

    NASA Astrophysics Data System (ADS)

    McCole, A. A.

    2003-12-01

    The recent expansion of Juniperus ashei (Ashe juniper) on the Edwards Plateau of Central Texas has important implications for the ecosystem structure, productivity and hydrology of the region. Ashe juniper expansion may negatively impact the ecology and hydrology of the Edwards Plateau. The Ashe juniper's morphology, rooting habit, and ability to photosynthesize throughout the year suggests greater water loss will occur in areas where Ashe juniper is prevalent compared to areas dominated by grasses. However, past studies have reached conflicting conclusions regarding Ashe juniper's effect on the water budget. A better understanding of the patterns of Ashe juniper's water use will aid in the understanding of how the Ashe juniper affects groundwater recharge, herbaceous productivity and evapotranspirational water loss. Stable isotopes of hydrogen and oxygen from precipitation, soil water, plant xylem water, and groundwater reveal the current ecosystem hydrology. A comparison of the isotopic compositions of potential water sources and juniper stem water indicates the source water utilized by the Ashe juniper. At the Honey Creek State Natural Area, Comal County, Texas the plant, soil and spring water as representative groundwater were sampled at approximately two month intervals over an annual cycle from two adjacent watersheds and analyzed for hydrogen and oxygen isotope composition. Soils were sampled at depth intervals of 5 to 10 cm and soil water content measured. Mass balance calculations using oxygen isotope data from the dry periods of the year, late summer and winter, indicate the Ashe juniper derives between 72% and 100% of it water from groundwater. In contrast, during the wet periods of the year, spring and fall, mass balance calculations indicate that between 45% and 100% of Ashe juniper's water is derived from soil water. Hydrogen isotope data from a subset of samples are consistent with these results. Bowens ratio measurements of evapotranspiration were

  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. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    NASA Astrophysics Data System (ADS)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.

  10. The sources of water in Martian meteorites: clues from hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Boctor, N. Z.; Alexander, C. M. O.'D.; Wang, J.; Hauri, E.

    2003-10-01

    H isotope measurements of carbonate, phosphate, feldspathic and mafic glasses, and post-stishovite silica phase in the shergottites Zagami, Shergotty, SaU 005, DaG 476, ALHA 77005 and EETA 79001, as well as in Chassigny and ALH 84001, show that all these phases contain deuterium-enriched water of extraterrestrial origin. The minerals and glasses analyzed may contain an initial primary hydrogen component, but their isotopic composition was modified to varying degrees by three different processes: interaction with a fractionated exchangeable water reservoir on Mars, hydrogen devolatilization by impact melting, and terrestrial contamination. Positive correlations between δD and water abundance in feldspathic glass and post-stishovite silica in Zagami, Shergotty, and SaU 005 is indicative of mixing of a high δD component (3000-4000‰) and a less abundant, low δD component (˜0‰). The high δD component is primarily derived from the Martian exchangable reservoir, but may also have been influenced by isotopic fractionation associated with shock-induced hydrogen loss. The low δD component is either a terrestrial contaminant or a primary "magmatic" component. The negative correlation between δD and water abundances in mafic and feldspathic glasses in ALH 84001, ALHA 77005, and EETA 79001 is consistent with the addition of a low δD terrestrial contaminant to a less abundant high-deuterium Martian component. The low δD of magmatic glass in melt inclusions suggests that the δD of Martian parent magma was low and that the initial H isotope signature of Mars may be similar to that of Earth.

  11. 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.

  12. 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.

  13. 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.

    1974-01-01

    Coordinated studies of the kinetics of crack growth and of hydrogen adsorption and diffusion were initiated to develop information that is needed for a clearer determination of the rate controlling process and possible mechanism for hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Inconel 718 alloy and 18Ni(200) maraging steel were selected for these studies. 18Ni(250) maraging steel, 316 stainless steel, and iron single crystal of (111) orientation were also included in the chemistry studies. Crack growth data on 18Ni(250) maraging steel from another program are included for comparison. No sustained-load crack growth was observed for the Inconel 718 alloy in gaseous hydrogen. Gaseous hydrogen assisted crack growth in the 18Ni maraging steels were characterized by K-independent (Stage 2) extension over a wide range of hydrogen pressures (86 to 2000 torr or 12 kN/m2 to 266 kN/m2) and test temperatures (-60 C to +100 C). The higher strength 18Ni(250) maraging steel was more susceptible than the lower strength 200 grade. A transition temperature was observed, above which crack growth rates became diminishingly small.

  14. Li adsorption, hydrogen storage and dissociation using monolayer MoS2: an ab initio random structure searching approach.

    PubMed

    Putungan, Darwin Barayang; Lin, Shi-Hsin; Wei, Ching-Ming; Kuo, Jer-Lai

    2015-05-01

    Utilizing ab initio random structure searching, we investigated Li adsorption on MoS2 and hydrogen molecules on Li-decorated MoS2. In contrast to graphene, Li can be adsorbed on both sides of MoS2, with even stronger binding than on the single side. We found that high coverages of Li can be attained without Li clustering, which is essential for hydrogen storage and Li ion batteries. Moreover, regarding battery applications, Li diffusion was also found to be easy. The fully-lithiated MoS2 can then adsorb H2 with 4.4 wt%. Interestingly, our calculations revealed that hydrogen molecules can be dissociated at high Li coverage with a minimal energy barrier. We further showed that the dissociated hydrogen atom can readily diffuse on the surface, thus keeping the reaction site active. We therefore propose that Li-MoS2 could be an inexpensive alternative catalyst to noble metals in hydrogen dissociation reactions. PMID:25849099

  15. 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.

  16. An instrumental and numerical method to determine the hydrogenic ratio in isotopic experiments in the TJ-II stellarator

    NASA Astrophysics Data System (ADS)

    Baciero, A.; Zurro, B.; Martínez, M.

    2014-11-01

    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 Hα and Dα 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.

  17. An instrumental and numerical method to determine the hydrogenic ratio in isotopic experiments in the TJ-II stellarator.

    PubMed

    Baciero, A; Zurro, B; Martínez, M

    2014-11-01

    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 Hα and Dα 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. PMID:25430312

  18. Predicting hydrogen isotope inventory in plasma-facing components during normal and abnormal operations in fusion devices

    NASA Astrophysics Data System (ADS)

    Hu, Alice; Hassanein, Ahmed

    2015-10-01

    Hydrogen isotope behavior and inventory in plasma-facing components (PFCs) of fusion devices are key concerns for safe, reliable, and economical operation. To accurately estimate hydrogen isotope retention and recovery in tungsten (the current leading candidate as a PFC), we have developed a model that was recently benchmarked against isotope depth profile and retention level in a tungsten target under various conditions and compared with both experimental data and simulation results. In this research, we have extended the model to include details of transient events. Therefore, one can use this model to estimate hydrogen isotope retention behavior in tungsten and potential other PFC candidates during normal operational pulse, effects of edge-localized modes (ELMs), and a possible cleaning processes scenario.

  19. 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.

  20. Isotope tracer investigation and ab-initio simulation of anisotropic hydrogen transport and possible multi-hydrogen centers in tin dioxide

    NASA Astrophysics Data System (ADS)

    Watanabe, Ken; Sakaguchi, Isao; Hashiguchi, Minako; Saito, Noriko; Ross, Emily M.; Haneda, Hajime; Ohsawa, Takeo; Ohashi, Naoki

    2016-06-01

    Hydrogen as an impurity in single crystals of tin dioxide was investigated through diffusivity and vibrational-mode analyses performed using isotope tracers and density functional theory calculations. It was found that hydrogen diffusion along the <001> axis is very fast, even at relatively low temperatures (400 °C), but is considerably slower within the (001) plane. Using transitional state calculations, this diffusion behavior was determined to be the result of anisotropy in the migration barrier for interstitial hydrogen (Hi). In addition, the two distinct vibrational modes observed in the optical spectrum were identified as the O-H stretching modes of Hi and the substitutional hydrogen at the tin sites.

  1. On-line high-precision stable hydrogen isotopic analyses on nanoliter water samples.

    PubMed

    Morrison, J; Brockwell, T; Merren, T; Fourel, F; Phillips, A M

    2001-08-01

    We describe a new on-line chromium reduction technique for the measurement of stable hydrogen (deltaD) isotopes in waters using continuous-flow isotope ratio mass spectrometry. The on-line Cr reduction method has low intersample memory effects (< 1%) and excellent precision and accuracy for deltaD (+/-0.5% and was used to analyze waters samples as small as 50 nL. The on-line Cr method has a number of significant advantages over conventional offline Zn and U reduction and on-line carbon-based pyrolysis techniques. A single Cr reactor can be used to analyze approximately 1,000 water samples using an injection volume of 0.5 microL, with an individual sample analysis time of 4 min. Intersample memory effects are negligible. The Cr reactor temperature of 1050 degree C is easily attainable on standard elemental analyzers and so does not require the specialized and costly high-temperature furnaces of carbon-based pyrolysis reactors. Furthermore, hydrogen isotopes in extremely small water samples in the 100-nL range or less can be easily measured; hence, this new method opens up a number of exciting application areas in earth and environmental sciences, for example, natural abundance deltaD measurements of individual fluid inclusions in geologic materials using a laser source and measurements of body fluids in physiological and metabolic research. PMID:11510820

  2. 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.

  3. Isotopic fractionation in proteins as a measure of hydrogen bond length

    NASA Astrophysics Data System (ADS)

    McKenzie, Ross H.; Athokpam, Bijyalaxmi; Ramesh, Sai G.

    2015-07-01

    If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor Φ is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate Φ as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric O-H⋯O bonds [R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the O-H stretch vibration, O-H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total Φ as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization Φ(R), used previously to determine bond lengths.

  4. Isotopic fractionation in proteins as a measure of hydrogen bond length.

    PubMed

    McKenzie, Ross H; Athokpam, Bijyalaxmi; Ramesh, Sai G

    2015-07-28

    If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor Φ is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate Φ as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric O-H⋯O bonds [R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the O-H stretch vibration, O-H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total Φ as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization Φ(R), used previously to determine bond lengths. PMID:26233131

  5. Hydrogen Explosion Analysis for Cold Source Installation at the High Flux Isotope Reactor

    SciTech Connect

    Cook, David Howard

    2008-01-01

    Installation of a cold neutron source in the High Flux Isotope Reactor (HFIR) involved introduction of pressurized, cryogenic hydrogen into the facility and created explosion hazards to reactor safety-related equipment and personnel. Evaluation of potential hydrogen releases and facility/personnel consequences as a result of explosions was a key part of the safety analyses submitted to the DOE to obtain approval for testing and operation with hydrogen. This paper involves a description of the various hydrogen release and explosion consequence analyses that were performed. The range of explosion calculations involved (1) a detonation analysis using a 2D-transient CTH code model, (2) various BLAST/FX code models to estimate structural damage from equivalent point TNT sources, (3) a BLASTX code model to propagate shock and gas flow overpressures from a point TNT source, (4) a spreadsheet that combined a TNT-quivalence model and strong deflagration methods, and (5) a hydrogen jet model to evaluate potential high pressure jet releases.

  6. Isotopic fractionation in proteins as a measure of hydrogen bond length

    SciTech Connect

    McKenzie, Ross H.; Athokpam, Bijyalaxmi; Ramesh, Sai G.

    2015-07-28

    If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor Φ is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate Φ as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric O–H⋯O bonds [R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the O–H stretch vibration, O–H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total Φ as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization Φ(R), used previously to determine bond lengths.

  7. Collective vibrational effects in hydrogen bonded liquid amides and proteins studied by isotopic substitution

    NASA Astrophysics Data System (ADS)

    Nielsen, O. F.; Johansson, C.; Christensen, D. H.; Hvidt, S.; Flink, J.; Høime Hansen, S.; Poulsen, F.

    2000-09-01

    Raman spectroscopy is used to study the fast dynamics of simple liquid amides and proteins. Raman spectra in the visible region of liquid amides are obtained with a triple additive scanning monochromator, whereas FT-Raman technique is used in the near-IR region in order to avoid fluorescence from impurities in the proteins. Raman spectra are shown in the amide-I region of HCONHCH 3 ( N-methylformamide with all isotopes in their natural abundance), H 13CONHCH 3, HC 18ONHCH 3, human growth hormone, frog tropomyosin and chymotrypsin inhibitor 2 including C-13 and N-15 enriched samples of the latter. Resonance energy transfer (RET) between amide molecules gives rise to a non-coincidence effect of the anisotropic and the isotropic components of the amide-I band. This effect influences the band position in mixtures of liquid amide isotopomers. A further spectral feature caused by collective vibrational modes in the hydrogen bonded liquid amides is named coalescence of bands in mixtures of isotopomers (CBMI). The result of this effect is that only one band is found in mixtures of isotopomers where bands at different frequencies are observed for each of the isotopomers. A similar effect may account for the observation of protein amide-I bands with frequencies dependent only on the secondary structure of the protein and not on the amino acid residues. RET and CBMI are due to a collectivity of vibrational modes in different amide molecules. This collectivity may be related to a cooperativity of hydrogen bonds. A low-frequency band around 100 cm -1 is observed in hydrogen bonded liquid amides and proteins. Isotopic substitution shows that the mode corresponding to this band involves displacements of atoms in hydrogen bonds. This mode may drive a breaking of the hydrogen bond.

  8. Hydrogen isotopes in individual amino acids reflect differentiated pools of hydrogen from food and water in Escherichia coli.

    PubMed

    Fogel, Marilyn L; Griffin, Patrick L; Newsome, Seth D

    2016-08-01

    Hydrogen isotope (δ(2)H) analysis is widely used in animal ecology to study continental-scale movement because δ(2)H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ(2)H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ(2)H values ranging from -55‰ to +1,070‰. The δ(2)H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ(2)H among AAs was nearly 200‰. The relative distributions of δ(2)H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ(2)H of nonessential AAs varied linearly with the δ(2)H of media water, whereas δ(2)H of essential AAs was nearly identical to δ(2)H in diet. Model calculations determined that as much as 46% of hydrogen in some nonessential AAs originated from water, whereas no more than 12% of hydrogen in essential AAs originated from water. These findings demonstrate that δ(2)H can route directly at the molecular level. We conclude that the patterns and distributions in δ(2)H of AAs are determined through biosynthetic reactions, suggesting that δ(2)H could become a new biosignature for studying novel microbial pathways. Our results also show that δ(2)H of AAs in an organism's tissues provides a dual tracer for food and environmental (e.g., drinking) water. PMID:27444017

  9. Cadmium isotope fractionation during adsorption to Mn oxyhydroxide at low and high ionic strength

    NASA Astrophysics Data System (ADS)

    Wasylenki, Laura E.; Swihart, Jared W.; Romaniello, Stephen J.

    2014-09-01

    We report results of experiments conducted to quantify the sense and magnitude of cadmium stable isotope fractionation during sorption to synthetic birnessite (Mn oxyhydroxide) and to constrain the molecular mechanism responsible for fractionation in this system. Ferromanganese crusts have recently been proposed as a possible archive of the cadmium isotopic composition of seawater over the last few tens of millions of years (Horner et al., 2010), and this archive can potentially yield information about biological use of Cd by diatoms over the Cenozoic Era. Cd isotopes may also be useful for determining the extent to which sorption to mineral substrates attenuates Cd transport in contaminated aquifers. At low ionic strength, we found a small fractionation effect (Δ114/112Cdfluid-solid = +0.12 ± 0.06‰, 1 sd; equivalent to +2.4 in terms of ε114/110Cd) that was constant as a function of the fraction of total Cd sorbed, indicating a reversible equilibrium isotope effect. At high ionic strength we observed a fractionation averaging (Δ114/112Cdfluid-solid = +0.27 ± 0.07‰ (1 sd; equivalent to +5.4 in terms of ε114/110Cd). A time series conducted at high ionic strength revealed that the magnitude of isotopic fractionation decreases gradually over time, from Δ114/112Cdfluid-solid of nearly +0.4‰ after 1 h to +0.2‰ after 24 h and +0.1‰ after 912 h. Furthermore, the percentage of Cd sorbed to birnessite increases over this interval from 27% to 58%. We hypothesize that this shift results from either changes over time in the structure and crystallinity of birnessite and/or a change in the molecular mechanism of sorption of cadmium on birnessite. Our result is encouraging for application of Cd isotopes in ferromanganese crusts to reconstruction of the Cd isotopic composition of coexisting seawater, given the very slow accumulation rates of such sediments.

  10. Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides

    NASA Astrophysics Data System (ADS)

    Nielsen, Sune G.; Wasylenki, Laura E.; Rehkämper, Mark; Peacock, Caroline L.; Xue, Zichen; Moon, Ellen M.

    2013-09-01

    We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (α ≈ 1.0002-1.0015, where α=205Tl/203Tl/205Tl/203Tl is smaller than observed between seawater and natural sediments (α ≈ 1.0019-1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65-81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297-313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated

  11. The setup of an extraction system coupled to a hydrogen isotopes distillation column

    SciTech Connect

    Zamfirache, M.; Bornea, A.; Stefanescu, I.; Bidica, N.; Balteanu, O.; Bucur, C.

    2008-07-15

    Among the most difficult problems of cryogenic distillation one stands apart: the extraction of the heavy fraction. By an optimal design of the cycle scheme, this problem could be avoided. A 'worst case scenario' is usually occurring when the extracted fraction consists of one prevalent isotope such as hydrogen and small amounts of the other two hydrogen isotopes (deuterium and/or tritium). This situation is further complicated by two parameters of the distillation column: the extraction flow rate and the hold-up. The present work proposes the conceptual design of an extraction system associated to the cryogenic distillation column used in hydrogen separation processes. During this process, the heavy fraction (DT, T{sub 2}) is separated, its concentration being the highest at the bottom of the distillation column. From this place the extraction of the gaseous phase can now begin. Being filled with adsorbent, the extraction system is used to temporarily store the heavy fraction. Also the extraction system provides samples for the gas Chromatograph. The research work is focused on the existent pilot plant for tritium and deuterium separation from our institute to validate the experiments carried out until now. (authors)

  12. Hydrogen Isotope Separation by Combined Electrolysis Catalytic Exchange Under Reduced Pressure

    SciTech Connect

    Sugiyama, T.; Asakura, Y.; Uda, T.; Abe, Y.; Shiozaki, T.; Enokida, Y.; Yamamoto, I.

    2005-07-15

    At the National Institute for Fusion Science experimental studies on hydrogen isotope separation by a Combined Electrolysis Catalytic Exchange (CECE) process have been carried out in order to apply it to the system of water detritiation for D-D burning experiments of the Large Helical Device. As an improvement of the CECE process, we have developed a reduced-pressure method as a means of enhancing the separation factor. The feasibility of this method is examined through application to a CECE process using a prototype separation column. Hydrogen-deuterium isotope separation experiments are performed in the two cases where column pressures are 12 and 101 kPa, and the separation factors for hydrogen and deuterium are obtained as 6.8 and 5.6, respectively. It is confirmed that the present method is applicable and useful to the CECE process. The values of Height Equivalent to a Theoretical Plate (HETP) are estimated by analyses with the equilibrium stage model. The HETP values are 15 cm at 12 kPa and 13 cm at 101 kPa. The increase of superficial velocity with decreasing pressure may spoil the efficiency of the mass transfer.

  13. Isotopic evidence for biogenic molecular hydrogen production in the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Walter, S.; Kock, A.; Steinhoff, T.; Fiedler, B.; Fietzek, P.; Kaiser, J.; Krol, M. C.; Popa, M. E.; Chen, Q.; Tanhua, T.; Röckmann, T.

    2015-10-01

    Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during five cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauretania. The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (-629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (-249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production a significant different source should be considered. The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors.

  14. Isotopic evidence for biogenic molecular hydrogen production in the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Walter, S.; Kock, A.; Steinhoff, T.; Fiedler, B.; Fietzek, P.; Kaiser, J.; Krol, M.; Popa, M. E.; Chen, Q.; Tanhua, T.; Röckmann, T.

    2016-01-01

    Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during 5 cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauritania.

    The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (-629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (-249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with the biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production, a significant different source should be considered.

    The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors.

  15. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    USGS Publications Warehouse

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  16. Isotope studies of hydrogen and oxygen in ground ice-experiences with the equilibration technique.

    PubMed

    Meyer, H; Schönicke, L; Wand, U; Hubberten, H W; Friedrichsen, H

    2000-01-01

    Equilibration technique suitable for a large amount of samples is described for hydrogen and oxygen isotope analyses of ground ice, especially ice wedges, including the sampling strategy and the analytical procedure as well as the calibration of the Finnigan MAT Delta-S mass spectrometer in June, 1999. Since for future analyses of ice wedges, a higher sampling resolution with limited sample volume is required, the limit of the equilibration technique for small water sample sizes of between 0.05 and 5 ml was checked. For water samples smaller than 1 ml, corresponding to a molar ratio [H2O]/[H2] of smaller than 0.994, a balance correction has to be applied. The experimental errors due to partial evaporation during evacuation, the balance calculation of the isotope equilibration process, the linearity as well as memory effects of the mass spectrometer for samples with large differences in delta18O and deltaD are tackled in this paper. In the polar regions of Northern Siberia without Late Pleistocene and Holocene glaciation, ground ice is used as an archive for paleoclimate studies. First results of stable isotope measurements on ice wedges clearly show a shift towards heavier isotopes and thus warmer winter temperatures as well as a change in the source of the precipitation between Late Pleistocene and Holocene. These results indicate the high potential of ground ice for paleoclimate studies. PMID:11077928

  17. Hydrogen Isotopic Composition of Water in the Martian Atmosphere and Released from Rocknest Fines

    NASA Technical Reports Server (NTRS)

    Leshin, L. A.; Webster, C. R.; Mahaffy, P. R.; Flesh, G. J.; Christensen, L. E.; Stern, J. C.; Franz, H. B.; McAdam, A. C.; Niles, P. B.; Archer, P. B., Jr.; Sutter, B.; Jones, J. H.; Ming, D. W.; Atreya, S. K.; Owen, T. C.; Conrad, P.

    2013-01-01

    The Mars Science Laboratory Curiosity rover sampled the aeolian bedform called Rocknest as its first solid samples to be analyzed by the analytical instruments CheMin and SAM. The instruments ingested aliquots from a sieved sample of less than 150 micrometer grains. As discussed in other reports at this conference [e.g., 1], CheMin discovered many crystalline phases, almost all of which are igneous minerals, plus some 10s of percent of x-ray amorphous material. The SAM instrument is focused on understanding volatiles and possible organics in the fines, performing evolved gas analysis (EGA) with the SAM quadrapole mass spectrometer (QMS), isotope measurements using both the QMS and the tunable laser spectrometer (TLS), which is sensitive to CO2, water and methane, and organics with the gas chromatograph mass spectrometer (GCMS). As discussed in the abstract by Franz et al. [2] and others, EGA of Rocknest fines revealed the presence of significant amounts of H2O as well as O-, C- and S-bearing materials. SAM has also tasted the martian atmosphere several times, analyzing the volatiles in both the TLS and QMS [e.g., 3,4]. This abstract will focus on presentation of initial hydrogen isotopic data from the TLS for Rocknest soils and the atmosphere, and their interpretation. Data for CO2 isotopes and O isotopes in water are still being reduced, but should be available by at the conference.

  18. Hydrogen isotope measurement of bird feather keratin, one laboratory's response to evolving methodologies.

    PubMed

    Fan, Majie; Dettman, David L

    2015-01-01

    Hydrogen in organic tissue resides in a complex mixture of molecular contexts. Some hydrogen, called non-exchangeable (H(non)), is strongly bound, and its isotopic ratio is fixed when the tissue is synthesized. Other pools of hydrogen, called exchangeable hydrogen (H(ex)), constantly exchange with ambient water vapor. The measurement of the δ(2)H(non) in organic tissues such as hair or feather therefore requires an analytical process that accounts for exchangeable hydrogen. In this study, swan feather and sheep wool keratin were used to test the effects of sample drying and capsule closure on the measurement of δ(2)H(non) values, and the rate of back-reaction with ambient water vapor. Homogenous feather or wool keratins were also calibrated at room temperature for use as control standards to correct for the effects of exchangeable hydrogen on feathers. Total δ(2)H values of both feather and wool samples showed large changes throughout the first ∼6 h of drying. Desiccant plus low vacuum seems to be more effective than room temperature vacuum pumping for drying samples. The degree of capsule closure affects exchangeable hydrogen equilibration and drying, with closed capsules responding more slowly. Using one control keratin standard to correct for the δ(2)H(ex) value for a batch of samples leads to internally consistent δ(2)H(non) values for other calibrated keratins run as unknowns. When placed in the context of other recent improvements in the measurement of keratin δ(2)H(non) values, we make recommendations for sample handing, data calibration and the reporting of results. PMID:25358407

  19. Carbon, hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Epstein, S.

    1982-01-01

    CCl4 and CH3OH solvent extractions were performed on the Murray, Murchison, Orgueil and Renazzo carbonaceous chondrites. Delta-D values of +300-+500% are found in the case of the CH3OH-soluble organic matter. The combined C, H and N isotope data makes it unlikely that the CH3OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relation between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water- and methanol-soluble organic compounds is suggested. Organic matter soluble in CCl4 has no N, and delta-C-13 values are lower than for CH3OH-soluble phases. It is concluded that there either are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.

  20. Systematics of isotopic production cross sections from interactions of relativistic {sup 40}Ca in hydrogen

    SciTech Connect

    Chen, C.; Guzik, T.G.; McMahon, M.; Wefel, J.P.; Albergo, S.; Caccia, Z.; Costa, S.; Insolia, A.; Potenza, R.; Russo, G.V.; Tuve, C.; Crawford, H.J.; Cronqvist, M.; Engelage, J.; Greiner, L.; Knott, C.N.; Waddington, C.J.; Lindstrom, P.J.; Tull, C.E.; Mitchell, J.W.; Webber, W.R.

    1997-09-01

    The isotopic production cross sections for {sup 40} Ca 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. {copyright} {ital 1997} {ital The American Physical Society}

  1. Hydrogen isotopes preclude marine hydrate CH4 emissions at the onset of Dansgaard-Oeschger events.

    PubMed

    Bock, Michael; Schmitt, Jochen; Möller, Lars; Spahni, Renato; Blunier, Thomas; Fischer, Hubertus

    2010-06-25

    The causes of past changes in the global methane cycle and especially the role of marine methane hydrate (clathrate) destabilization events are a matter of debate. Here we present evidence from the North Greenland Ice Core Project ice core based on the hydrogen isotopic composition of methane [deltaD(CH4)] that clathrates did not cause atmospheric methane concentration to rise at the onset of Dansgaard-Oeschger (DO) events 7 and 8. Box modeling supports boreal wetland emissions as the most likely explanation for the interstadial increase. Moreover, our data show that deltaD(CH4) dropped 500 years before the onset of DO 8, with CH4 concentration rising only slightly. This can be explained by an early climate response of boreal wetlands, which carry the strongly depleted isotopic signature of high-latitude precipitation at that time. PMID:20576890

  2. Hydrogen chloride 37Cl/35Cl isotopic ratio field analyzer for the investigation of volcanic plumes

    NASA Astrophysics Data System (ADS)

    D'Amato, Francesco; Burton, Mike; Chiarugi, Antonio; Viciani, Silvia

    2015-04-01

    We present a new analyzer for the in-field measurement of the isotopic ratio 37Cl/35Cl in the hydrogen chloride emitted by volcanoes, developed within the frame of the ERC Project CO2Volc (Grant 279802). The Project aims to the measurement of several molecular species in the volcanic plumes. The analyzer is based on molecular spectroscopy. The volcanic plume interacts in a multipass cell with two laser beams at suitable wavelengths. From the absorptions of the two beams by the two isotopologues the isotopic ratio is retrieved. We report here the results of the laboratory checks of the instrument, and the results of a measurement campaign carried out on Etna and Vulcano. The campaign aimed to verify not only the in-field performances of the analyzer but also to assess its robustness in such a hostile environment.

  3. Hydrogen-isotope evidence for extrusion mechanisms of the Mount St Helens lava dome

    NASA Technical Reports Server (NTRS)

    Anderson, Steven W.; Fink, Jonathan H.

    1989-01-01

    Hydrogen isotope analyses were used to determine water content and deuterium content for 18 samples of the Mount St Helens dome dacite in an attempt to identify the triggering mechanisms for periodic dome-building eruptions of lava. These isotope data, the first ever collected from an active lava dome, suggest a steady-state process of magma evolution combining crystallization-induced volatile production in the chamber with three different degassing mechanisms: closed-system volatile loss in the magma chamber, open-system volatile release during ascent, and kinetically controlled degassing upon eruption at the surface. The data suggest the future dome-building eruptions may require a new influx of volatile-rich magma into the chamber.

  4. Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

    NASA Astrophysics Data System (ADS)

    Kreuzer-Martin, H. W.; Hegg, E. L.

    2008-12-01

    Intracellular water is an important pool of oxygen and hydrogen atoms for biosynthesis. Intracellular water is usually assumed to be isotopically identical to extracellular water, but an unexpected experimental result caused us to question this assumption. Heme O isolated from Escherichia coli cells grown in 95% H218O contained only a fraction of the theoretical value of labeled oxygen at a position where the O atom was known to be derived from water. In fact, fewer than half of the oxygen atoms were labeled. In an effort to explain this surprising result, we developed a method to determine the isotope ratios of intracellular water in cultured cells. The results of our experiments showed that during active growth, up to 70% of the oxygen atoms and 50% of the hydrogen atoms in the intracellular water of E. coli are generated during metabolism and can be isotopically distinct from extracellular water. The fraction of isotopically distinct atoms was substantially less in stationary phase and chilled cells, consistent with our hypothesis that less metabolically-generated water would be present in cells with lower metabolic activity. Our results were consistent with and explained the result of the heme O labeling experiment. Only about 40% of the O atoms on the heme O molecule were labeled because, presumably, only about 40% of the water inside the cells was 18O water that had diffused in from the culture medium. The rest of the intracellular water contained 16O atoms derived from either nutrients or atmospheric oxygen. To test whether we could also detect metabolically-derived hydrogen atoms in cellular constituents, we isolated fatty acids from log-phase and stationary phase E. coli and determined the H isotope ratios of individual fatty acids. The results of these experiments showed that environmental water contributed more H atoms to fatty acids isolated in stationary phase than to the same fatty acids isolated from log-phase cells. Stable isotope analyses of

  5. Hydrogen isotopes in lunar volcanic glasses and melt inclusions reveal a carbonaceous chondrite heritage.

    PubMed

    Saal, Alberto E; Hauri, Erik H; Van Orman, James A; Rutherford, Malcolm J

    2013-06-14

    Water is perhaps the most important molecule in the solar system, and determining its origin and distribution in planetary interiors has important implications for understanding the evolution of planetary bodies. Here we report in situ measurements of the isotopic composition of hydrogen dissolved in primitive volcanic glass and olivine-hosted melt inclusions recovered from the Moon by the Apollo 15 and 17 missions. After consideration of cosmic-ray spallation and degassing processes, our results demonstrate that lunar magmatic water has an isotopic composition that is indistinguishable from that of the bulk water in carbonaceous chondrites and similar to that of terrestrial water, implying a common origin for the water contained in the interiors of Earth and the Moon. PMID:23661641

  6. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Astrophysics Data System (ADS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, S.

    1995-09-01

    Carbon, hydrogen and sulfur isotopic measurements have been made on individual members of a recently discovered class of organic sulfur compounds, alkyl sulfonates, in the Murchison meteorite. Cooper and Chang (1) reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into potential synthetic mechanisms of these, and possibly other, organic species. Hydrogen isotopic measurements of the sulfonates now reveal deuterium excesses ranging from +660 to +2730 per mil. 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. Measurement 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 (2) have shown that some bulk ureilites possess excess 33S and Thiemens et al. (3) have reported excess 33S in an oldhamite separate from Norton County. Rees and Thode (4) reported a large 33S excess in an Allende acid residue, however, attempts to verify this measurement have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect nebular chemistry, identification of potential carriers is of considerable interest. In the present study the three stable isotopes of sulfur were measured in methane sulfonate extracted from the Murchison meteorite. The isotopic composition was found to be delta 33S=2.48, delta 34S=2.49 and delta 36S = 6.76 per mil. Based upon analysis of more than 60 meteoritic, and numerous terrestrial samples, the mass fractionation lines are defined by 33Delta = delta 33S-0.50 delta 34S and 36Delta = delta 36S -1.97 delta 34S. From these relations a 33Delta = 1.24 per mil and 36Delta = 0.89 per mil is observed. These anomalies

  7. Influence of thermal maturity on the hydrogen isotope content of extractable hydrocarbons

    NASA Astrophysics Data System (ADS)

    Radke, J.; Bechtel, A.; Püttmann, W.; Gleixner, G.

    2003-04-01

    Based on hydrogen isotope analysis of hydrocarbons from recent sediments it is suggested that compound specific hydrogen isotope ratios are a new proxy to reconstruct the palaeoclimate (Sauer et al., 2001). However, it remains unclear if transformation of carbon bound hydrogen with environmental water during maturation or thermal methanogenesis might influence the observed values. Short-term experiments excluded exchange reactions of deuterium from alkanes (Schimmelmann et al., 1999), however, thermally stressed kerogens are enriched in deuterium (Schoell, 1984). Therefore, we investigated the influence of maturity on the deltaD-values of alkanes and acyclic isoprenoids. In the Kupferschiefer horizon from the Polish Zechstein Basin thermal maturity of organic matter is correlated to burial depth yielding a natural long-term exchange experiment. The deltaD-values of extracted hydrocarbons linearly correlated with thermal maturity. These results enable the correction of deltaD values from biomarkers with known maturity and therefore expanding palaeoclimatic reconstructions using deltaD values to the geological past. References: SAUER, P.E., EGLINTON, T.I., HAYES, J.M., SCHIMMELMANN, A. &SESSIONS, A.L. (2001) Compound specific D/H ratios of lipid biomarkers from sediments as a proxy for environmental and climatic conditions. Geochimica et Cosmochimica Acta, 65(2), 213-222. SCHIMMELMANN, A., LEWAN, M.D. &WINTSCH, R.P. (1999) D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III. Geochimica et Cosmochimica Acta, 63(22), 3751-3766. SCHOELL, M. (1984) Wasserstoff- und Kohlenstoffisotope in organischen Substanzen, Erdölen und Erdgasen. Schweitzerbart'sche Verlagsbuchhandlung, Stuttgart. Reihe D (67), 161pp.

  8. Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models

    USGS Publications Warehouse

    Berndt, M.E.; Seal, R.R., II; Shanks, Wayne C., III; Seyfried, W.E., Jr.

    1996-01-01

    Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H2O fluids at temperatures ranging from 399-450??C and pressures from 277-397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 ln ??(vap-brine) = 2.54(??0.83) + 2.87(??0.69) x log (??P), where ??(vap-brine) is the fractionation factor and ??P is a pressure term representing distance from the critical curve in the NaCl/H2O system. The effect of phase separation on hydrogen isotope distribution in subseafloor hydrothermal systems depends on a number of factors, including whether phase separation is induced by heating at depth or by decompression of hydrothermal fluids ascending to the seafloor. Phase separation in most subseafloor systems appears to be a simple process driven by heating of seawater to conditions within the two-phase region, followed by segregation and entrainment of brine or vapor into a seawater dominated system. Resulting vent fluids exhibit large ranges in Cl concentration with no measurable effect on ??D. Possible exceptions to this include hydrothermal fluids venting at Axial and 9??N on the East Pacific Rise. High ??D values of low Cl fluids venting at Axial are consistent with phase separation taking place at relatively shallow levels in the oceanic crust while negative ??D values in some low Cl fluids venting at 9??N suggest involvement of a magmatic fluid component or phase separation of D-depleted brines derived during previous hydrothermal activity.

  9. Hydrogen isotopic compositions of organic compounds in plants reflect the plant's carbon metabolism

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    The main factors controlling δ2H of plant organic compounds are generally assumed to be the plant's source water and the evaporative deuterium enrichment of leaf water. Hydrogen isotope analyses of plant compounds from sediments or tree rings are therefore mainly applied to assess hydrological conditions at different spatial and temporal scales. However, the biochemical hydrogen isotope fractionation occurring during biosynthesis of plant organic compounds (ɛbio) also accounts for a large part of the variability observed in the δ2H values. Nevertheless, only few studies have directly addressed the physiological basis of this variability and even fewer studies have thus explored possible applications of hydrogen isotope variability in plant organic compounds for plant physiological research. Here we show two datasets indicating that the plant's carbon metabolism can have a substantial influence on δ2H values of n-alkanes and cellulose. First, we performed a controlled experiment where we forced plants into heterotrophic and autotrophic C-metabolism by growing them under four different light treatments. Second, we assessed the δ2H values of different parasitic heterotrophic plants and their autotrophic host plants. Our two datasets show a systematic shift in ɛbio of up to 80 ‰ depending on the plant's carbon metabolism (heterotrophic or autotrophic). Differences in n-alkane and cellulose δ2H values in plants with autotrophic vs. heterotrophic metabolisms can be explained by different NADPH pools that are used by the plants to build their compounds either with assimilates that originate directly from photosynthesis or from stored carbohydrates. Our results have significant implications for the calibration and interpretation of geological records. More importantly, as the δ2H values reflect the plant's carbon metabolism involved during the tissue formation, our findings highlight the potential of δ2H values as new tool for studying plant and ecosystem carbon

  10. Carbon and hydrogen isotope fractionation by microbial methane oxidation: Improved determination

    SciTech Connect

    Mahieu, Koenraad . E-mail: Koenraad.Mahieu@Ugent.be; Visscher, Alex De; Vanrolleghem, Peter A.; Cleemput, Oswald Van

    2006-07-01

    Isotope fractionation is a promising tool for quantifying methane oxidation in landfill cover soils. For good quantification an accurate determination of the isotope fractionation factor ({alpha}) of methane oxidation based on independent batch experiments with soil samples from the landfill cover is required. Most studies so far used data analysis methods based on approximations of the Rayleigh model to determine {alpha}. In this study, the two most common approximations were tested, the simplified Rayleigh approach and the Coleman method. To do this, the original model of Rayleigh was described in measurable variables, methane concentration and isotopic abundances, and fitted to batch oxidation data by means of a weighted non-linear errors-in-variables regression technique. The results of this technique were used as a benchmark to which the results of the two conventional approximations were compared. Three types of batch data were used: simulated data, data obtained from the literature, and data obtained from new batch experiments conducted in our laboratory. The Coleman approximation was shown to be acceptable but not recommended for carbon fractionation (error on {alpha} - 1 up to 5%) and unacceptable for hydrogen fractionation (error up to 20%). The difference between the simplified Rayleigh approach and the exact Rayleigh model is much smaller for both carbon and hydrogen fractionation (error on {alpha} - 1 < 0.05%). There is also a small difference when errors in both variables (methane concentration and isotope abundance) are accounted for instead of assuming an error-free independent variable. By means of theoretical calculations general criteria, not limited to methane, {sup 13}C, or D, were developed for the validity of the simplified Rayleigh approach when using labelled compounds.

  11. Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

    PubMed

    Tamburri, Emanuela; Cassani, Maria Cristina; Ballarin, Barbara; Tomellini, Massimo; Femoni, Cristina; Mignani, Adriana; Terranova, Maria Letizia; Orlanducci, Silvia

    2016-05-23

    Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions. PMID:27094213

  12. Adsorption and Diffusion of Hydrogen in a New Metal-Organic Framework Material: [Zn(bdc)(ted)0.5

    SciTech Connect

    Liu, J.; Lee, J.Y.; Pan, L.; Obermyer, R.T.; Simizu, S.; Zande, B.; Li, J.; Sankar, S.G.; Johnson, J.K

    2008-02-28

    We have experimentally measured hydrogen isotherms at 77 and 298 K up to a hydrogen pressure of 50 bar in a recently developed metal-organic framework material, [Zn(bdc)(ted)0.5] (bdc ) benzenedicarboxylate, ted ) triethylenediamine). This material has a tetragonal structure and relatively small pores. We have used atomically detailed simulations to compute adsorption isotherms of hydrogen over the same temperature and pressure ranges studied experimentally. The agreement between experiments and simulations is very good. We have included quantum effects through the Feynman-Hibbs effective potential approach; quantum effects must be included at 77 K to achieve agreement with experiments. We have used equilibrium molecular dynamics to compute self- and transport diffusivities of hydrogen in [Zn(bdc)(ted)0.5] at both 77 and 298 K over a range of pore loadings. Quantum effects are found to decrease the self-diffusivity compared with classical simulations at fixed loading. Conversely, at fixed pressure, quantum effects lead to a lower loading and therefore a higher self-diffusion coefficient compared with classical simulation results. Transport diffusivities with and without quantum corrections are essentially indistinguishable. The diffusivities for H2 in [Zn(bdc)-(ted)0.5] are comparable to H2 in IRMOF-1 at 298 K.

  13. Hydrogen adsorption and storage of Ca-decorated graphene with topological defects: A first-principles study

    NASA Astrophysics Data System (ADS)

    Ma, Ling; Zhang, Jian-Min; Xu, Ke-Wei; Ji, Vincent

    2014-09-01

    As a candidate for hydrogen storage medium, geometric stability and hydrogen capacity of Ca-decorated graphene with topological defects are investigated using the first-principle based on density functional theory (DFT), specifically for the experimentally realizable single carbon vacancy (SV), 585 double carbon vacancy (585 DCV) and 555-777 double carbon vacancy (555-777 DCV) defects. It is found that Ca atom can be stabilized on above defective graphenes since Ca's binding energy on vacancy defect is much larger than its cohesive energy. Up to six H2 molecules can stably bind to a Ca atom on defective graphene with the average adsorption energies of 0.17-0.39 eV/H2. The hybridization of the Ca-3d orbitals with H2-σorbitals and the electrostatic interaction between the Ca cation and the induced H2 dipole both contribute to the H2 molecules binding. Double-side Ca-decorated graphene with 585 DCV and 555-777 DCV defects can theoretically reach a gravimetric capacity of 5.2 wt% hydrogen, indicating that Ca-decorated defective graphene can be used as a promising material for high density hydrogen storage.

  14. Water masses along the OVIDE 2010 section as identified by oxygen and hydrogen stable isotope values

    NASA Astrophysics Data System (ADS)

    Voelker, Antje; Salgueiro, Emilia; Thierry, Virginie

    2016-04-01

    The OVIDE transect between the western Iberian Peninsula and the southern tip of Greenland is one of the hydrographic sections in the North Atlantic that is measured regularly to identify changes in water mass formation and transport and thus to evaluate the state of the Atlantic Meridional Overturning Circulation (Mercier et al., 2015; García-Ibáñez et al., 2015; both in Progr. in Oceanography). During the OVIDE 2010 campaign seawater samples covering the complete water column were collected on the section between Portugal and the Reykjanes ridge for stable isotope analyses. Oxygen (δ18O) and hydrogen (δD) stable isotope values were measured simultaneously by cavity ring-down laser spectroscopy using a L1102-i Picarro water isotope analyser at the Godwin Laboratory for Paleoclimate Research (Univ. Cambridge, UK). Within the upper water column the stable isotope values clearly mark the positions of the Portugal Current (40.3°N 11°W), the North Atlantic Drift (46.2°N 19.4°W) and of the subarctic front (51°N 23.5°W). Up to Station 36 (47.7°N 20.6°W) an upper (around 600 m) and lower (around 1000 m) branch of the Mediterranean Outflow water (MOW) can clearly be distinguished by high oxygen (0.5-0.7‰) and hydrogen (3-5‰) values. At Station 28 (42.3°N 15.1°W) strong MOW influence is also indicated between 1400 and 1600 m. In the west European Basin, lower oxygen isotope values reveal the presence of Labrador Sea Water (LSW) below the MOW (down to 2200 m). Close to and west of the subarctic front this water mass shallows and occupies the complete interval between 1000 and 2000 m water depth. In the Iceland basin, two additional levels with lower oxygen isotope values are observed. The deeper level (2200-3500 m) marks Iceland Scotland Overflow Water (ISOW) that based on its distinct isotopic signature (δ18O ≤ 0.25‰) can be traced as far east as 18.5°W (down to at least 3500 m). Close to the Reykjanes ridge both, the ISOW and LSW, are also

  15. Relative Humidity Recorded in the hydrogen and oxygen isotopic compositions of treerings

    NASA Astrophysics Data System (ADS)

    Shu, Y.; Feng, X.

    2002-12-01

    Many paleoclimate proxies have been developed to reconstruct continental surface temperatures. Examples are oxygen or hydrogen isotope ratios in ice cores, groundwater, and treerings, oxygen isotopes in stalagmites, tree-ring width and density, and pollen distributions in lake sediment cores. Several proxies listed above are also indicative of amount of precipitation. However, to our knowledge, a proxy indicator for air humidity does not yet exist. Humidity is related to the moisture content in the atmosphere, which plays an important role in the energy budget determining the planetary climate. Here we describe a study of oxygen and hydrogen isotopic compositions in modern treerings collected from trees growing along a transect of precipitation in Olympic Peninsula, Washington, USA. We are consciously optimistic that reconstruction of relative humidity may be possible if both oxygen and hydrogen isotopic compositions in tree cellulose are determined. Douglas-fir (Pseudotsuga menziesii) and subalpine fir (Abies lasiocarpa) trees were sampled at five sites within the Olympic Mountains. Among these sites, the annual precipitation varies from over three meters on the westside of the mountains to less than one meter on the eastside. The δ18O and δD in the surface water of these sites follow the trend of precipitation, decreasing from west to east. Annual treerings from seven trees were analyzed for δ18O and δD values. The number of rings from each tree ranges from 23 (1963-1985) to 48 (1949-1996). No significant correlation was found between the δD and δ18O values within each tree. This is expected because the range of variation in the isotopic ratios of source water at a given site is limited, and other factors such as humidity and soil hydrology may upset the one-to-one relationship between the δD and δ18O in the source water and those in treerings. However, the mean δD and δ18O values from each tree are weakly correlated with a slope of 19. This slope is

  16. Practically convenient and industrially-aligned methods for iridium-catalysed hydrogen isotope exchange processes.

    PubMed

    Cochrane, A R; Idziak, C; Kerr, W J; Mondal, B; Paterson, L C; Tuttle, T; Andersson, S; Nilsson, G N

    2014-06-14

    The use of alternative solvents in the iridium-catalysed hydrogen isotope exchange reaction with developing phosphine/NHC Ir(I) complexes has identified reaction media which are more widely applicable and industrially acceptable than the commonly employed chlorinated solvent, dichloromethane. Deuterium incorporation into a variety of substrates has proceeded to deliver high levels of labelling (and regioselectivity) in the presence of low catalyst loadings and over short reaction times. The preparative outputs have been complemented by DFT studies to explore ligand orientation, as well as solvent and substrate binding energies within the catalyst system. PMID:24756541

  17. Climatic implications of an 8000-year hydrogen isotope time series from bristlecone pine trees

    SciTech Connect

    Feng, X.; Epstein, S. )

    1994-08-19

    Tree rings from three dendrochronologically dated bristlecone pines were analyzed for stable hydrogen isotopic composition. These trees give a continuous time series from 8000 years ago to the present that indicates the presence of a postglacial climate optimum 6800 years ago and a continuous cooling since then. The qualitative agreement between this record and records from other sources, such as ice cores, pollen, and treeline fluctuations, indicates that these climate changes were global. This record can serve as a reference for other climate indicators throughout the past 8000 years.

  18. Study of hydrogen isotopes behavior in tungsten by a multi trapping macroscopic rate equation model

    NASA Astrophysics Data System (ADS)

    Hodille, E. A.; Ferro, Y.; Fernandez, N.; Becquart, C. S.; Angot, T.; Layet, J. M.; Bisson, R.; Grisolia, C.

    2016-02-01

    Density functional theory (DFT) studies show that in tungsten a mono vacancy can contain up to six hydrogen isotopes (HIs) at 300 K with detrapping energies varying with the number of HIs in the vacancy. Using these predictions, a multi trapping rate equation model has been built and used to model thermal desorption spectrometry (TDS) experiments performed on single crystal tungsten after deuterium ions implantation. Detrapping energies obtained from the model to adjust temperature of TDS spectrum observed experimentally are in good agreement with DFT values within a deviation below 10%. The desorption spectrum as well as the diffusion of deuterium in the bulk are rationalized in light of the model results.

  19. Site selective syntheses of [(3)H]omeprazole using hydrogen isotope exchange chemistry.

    PubMed

    Pollack, Scott R; Schenk, David J

    2015-01-01

    Omeprazole (Prilosec®) is a selective and irreversible proton pump inhibitor used to treat various medical conditions related to the production of excess stomach acids. It functions by suppressing secretion of those acids. Radiolabeled compounds are commonly employed in the drug discovery and development process to support efforts including library screening, target identification, receptor binding, assay development and validation and safety assessment. Herein, we describe synthetic approaches to the controlled and selective labeling of omeprazole with tritium via hydrogen isotope exchange chemistry. The chemistry may also be used to prepare tritium labeled esomeprazole (Nexium®), the active pure (S)-enantiomer of omeprazole. PMID:26380956

  20. Compound-Specific Hydrogen Isotope Ratios Record Late-Quaternary Temperature Changes at Crooked Pond, Massachusetts.

    NASA Astrophysics Data System (ADS)

    Shuman, B. N.; Huang, Y.; Wang, Y.; Webb, T.

    2001-12-01

    We show that compound-specific hydrogen isotope ratios from sedimentary biomarkers (organic compounds produced by aquatic algae) provide a useful record of past climate. The biomarkers preserve the hydrogen isotopic composition of lake water, which is controlled by annual and seasonal changes in the temperature of precipitation, evaporation, and the path of moisture transport. A transect of lake water and modern sediment samples from Ontario to Florida reveals parallel 100 per mille shifts in the δ D values of the lake water and sedimentary biomarkers. The water and biomarker hydrogen isotope ratios follow a linear relationship with a slope of ~1 (correlation coefficient of 0.93). The correlation between δ D values of the biomarkers and annual mean temperature is, therefore, also linear (correlation coefficient of 0.85). Consistent trends were revealed by an analysis of sedimentary biomarkers in a core spanning ca. 15,000 years, from Crooked Pond, a small closed kettle lake in Massachusetts. The pond is an outcrop of groundwater in a glacial alluvium aquifer, with a large aquifer-to-surface-exposure ratio ( ~100). The aquifer is recharged mainly by local precipitation and its water has a residence time of a decade or less. Therefore, the analysis of the biomarkers showed hydrogen isotope ratios that were 1) minimally influenced by evaporation and 2) reflected century- and longer scale changes in the temperature of precipitation. The δ D record is consistent with quantitative estimates of temperature, based on fossil pollen data. The δ D values increase ~65 per mille from 15,000 to 5000 cal yr B.P., with a negative 25-50 per mille excursion during the cold Younger Dryas interval (12,900-11,600 cal yr B.P.). A positive δ D shift of 15 per mille records warming after the collapse of the Laurentide ice sheet (ca. 8000 cal yr B.P); and, a gradual cooling during the late Holocene is captured by a steady decline in δ D values.

  1. About Tagish Lake as a Potential Parent Body for Polar Micrometeorites; Clues from their Hydrogen Isotopic Compositions

    NASA Technical Reports Server (NTRS)

    Engrand, C.; Gounelle, M.; Zolensky, M. E.; Duprat, J.

    2003-01-01

    The origin of the Antarctic micrometeorites (AMMs) is still a matter of debate. Their closest meteoritic counterparts are the C2 chondrites, but the match is not perfect, and the parent body(ies) of the AMMs is(are) still to be identified. Tagish Lake is a new meteorite fall which bears similarity with CI1 and CM2 chondrites, but is distinct from both. Based on the mineralogy of phyllosilicates, Noguchi et al. proposed that the phyllosilicate-rich AMMs and the Tagish Lake meteorites could derive from similar asteroids. The hydrogen isotopic compositions of extra-terrestrial samples can be used to get some insight on their origin. The D/H ratios of AMMs and of Tagish Lake have been measured, but using different analytical techniques. They are therefore not directly comparable. We performed additional hydrogen isotopic analyses of fragments of Tagish Lake using the same experimental setup previously used for the measurement of the hydrogen isotopic composition of AMMs. In this work, we could also analyze separately both lithologies of Tagish Lake (carbonate-poor and -rich). The distributions of delta D values measured in the two lithologies of Tagish Lake are very similar, indicating that fluids with similar hydrogen isotopic compositions altered the meteorite on the parent body for the two lithologies. Yet, the hydrogen isotopic composition of Tagish Lake is different from that of AMMs, suggesting that they do not derive from the same parent body.

  2. Experimental Abiogenic Synthesis and Stable Carbon and Hydrogen Isotope Values of Gaseous Hydrocarbons and the Implications for Identifying Biosignatures

    NASA Astrophysics Data System (ADS)

    Morrill, P. L.; Weinberger, D. S.; Sherwood Lollar, B.; Fogel, M. L.; Cody, G. D.

    2006-12-01

    While geochemical indicators or `biosignatures', such as stable carbon and hydrogen isotope values, of biogenic hydrocarbons have been identified, less is known about unambiguous abiogenic hydrocarbons, because they are rare and, until recently, difficult to create in laboratory experiments. Traditionally, hydrocarbons that are depleted in 13C are considered to be of biogenic origin, because many biological enzymatic reactions are known to preferentially incorporate the lighter carbon isotope. In this study, laboratory experiments were designed to determine the conditions under which abiogenic hydrocarbons are formed, and if a similar carbon isotopic depletion would be observed during their abiogenic synthesis. Experimentally, carbon dioxide was reduced in the presence of a metal catalyst under hydrothermal conditions in sealed gold capsules. All experiments were performed at 250 C. Two different metal catalysts were used, iron powder and awaurite, a range of pressures from 500 to 2000 bars were tested, and two time series were performed from 1 to 20 hrs, one with pure formic acid and the other with a 1:1 ratio of formic acid and water. Both iron powder and awaurite were excellent catalysts. Hydrocarbon chains up to 7 carbons long were produced. It was found that the concentration of methane increased with catalytic surface area, suggesting that the reactions are surfaced catalyzed. Reactions at lower pressures created longer chain hydrocarbons. At 2000 bars gaseous mixtures were primarily composed of methane and ethane, with lesser amounts of propane. The abiogenic gaseous hydrocarbons had relatively large carbon isotopic depletions, which mimic that of gases with biogenic origins. Hydrogen isotopes were also measured. A hydrogen isotopic enrichment trend was observed with each additional carbon. A similar hydrogen isotopic enrichment was also seen in Canadian Shield hydrocarbons interpreted as abiogenic. This experimental data further emphases the need for both

  3. Solar flare accelerated isotopes of hydrogen and helium. [observed by IMP-4 and IMP-5

    NASA Technical Reports Server (NTRS)

    Anglin, J. D.; Dietrich, W. F.; Simpson, J. A.

    1973-01-01

    Measurements of solar flare hydrogen, deuterium, tritium, helium-3, and helium-4 in the energy range approximately 10 to 50 MeV per nucleon obtained with instrumentation on the IMP-4 and IMP-5 satellites are reported and studies based on these results which place several constraints on theories of solar flare particle acceleration are discussed. A brief review of previous work and the difficulties in studying the rare isotopes of hydrogen and helium is also included. Particular emphasis is placed on the fact that the information to be obtained from the solar flare products of high energy interactions is not available through either solar wind observations where both the acceleration mechanism and the coronal source of the nuclear species are different, or optical measurements of solar active regions.

  4. Multisample conversion of water to hydrogen by zinc for stable isotope determination

    USGS Publications Warehouse

    Kendall, C.; Coplen, T.B.

    1985-01-01

    Two techniques for the conversion of water to hydrogen for stable isotope ratio determination have been developed that are especially suited for automated multisample analysis. Both procedures involve reaction of zinc shot with a water sample at 450 ??C. in one method designed for water samples in bottles, the water is put in capillaries and is reduced by zinc in reaction vessels; overall savings in sample preparation labor of 75% have been realized over the standard uranium reduction technique. The second technique is for waters evolved under vacuum and is a sealed-tube method employing 9 mm o.d. quartz tubing. Problems inherent with zinc reduction include surface inhomogeneity of the zinc and exchange of hydrogen both with the zinc and with the glass walls of the vessels. For best results, water/zinc and water/glass surface area ratios of vessels should be kept as large as possible.

  5. First-Principles Studies of Hydrogen Adsorption at Pd-SiO2 Interfaces

    PubMed Central

    Irokawa, Yoshihiro; Usami, Mamoru

    2015-01-01

    The interaction of hydrogen with Pd-SiO2 interfaces has been investigated for the first time using first-principles calculations based on density functional theory. The hydrogen-induced polarization at the Pd-SiO2 interfaces was evaluated using Pd-SiO2 interface supercells. As a result, the potential change induced by interfacial hydrogen atoms was not observed even for hydrogen concentration of ~1.3 × 1015 cm−2 at the Pd-SiO2 interface. This result implies that hydrogen does not create an electric double layer at the Pd-SiO2 interface but change the property of the SiO2 region, resulting in the hydrogen sensitivity of the devices. PMID:26110410

  6. Experimental studies of hydrogen on boron nitride: I. Adsorption isotherms of HD

    SciTech Connect

    Evans, M.D.; Sullivan, N.S.

    1995-09-01

    The authors report the results of measurements of adsorption isotherms of deuterium hydride (HD) adsorbed onto boron nitride. From this data they derive both the two-dimensional critical point temperatures (using Larher`s method) and the heat of adsorption for the first few layers of this system. These results are compared with similar measurements of HD adsorbed onto graphite and MgO. While substantial substeps within some adlayer steps are evident in the adsorption isotherms of HD on graphite and MgO and have been shown to indicate a two-dimensional liquid-solid transition within the layer, no substep is evident at the level of one percent of a step level for HD adsorbed onto BN.

  7. Hydrogen isotope analyses of alteration phases in the nakhlite martian meteorites

    NASA Astrophysics Data System (ADS)

    Hallis, L. J.; Taylor, G. J.; Nagashima, K.; Huss, G. R.; Needham, A. W.; Grady, M. M.; Franchi, I. A.

    2012-11-01

    Secondary alteration phases, such as carbonates, smectite clays and Fe-oxides, are found within the martian meteorites. If these meteorites were seen to fall, the assumption can be reasonably made that the secondary phases have a martian origin. However, for martian meteorite finds, this is not the case. Deuterium/hydrogen (D/H) ratio analysis can be used to distinguish between terrestrial and martian secondary alteration phases - the martian atmosphere is currently five times enriched in deuterium compared to terrestrial seawater, producing a deuterium enrichment in the martian alteration phases large enough to be detected with modern ion microprobe techniques. We aimed to measure the D/H ratio of the iddingsite-like alteration veins in the nakhlite martian meteorites Nakhla, MIL 03346, MIL 090030 and Y 000593, to help confirm the martian origin of this material, and determine the relative amounts of terrestrial contamination in each meteorite. As an observed fall Nakhla is nominally uncontaminated by terrestrial alteration, and shows elevated δD values in its alteration veins. However, even the highest of these values is much below that of the martian atmosphere, indicating that terrestrial contamination, probably combined with fractionation effects between the martian atmosphere and the alteration material, have reduced the δD values of these veins. The speed of hydrogen isotope exchange in the nakhlite iddingsite-like alteration veins is demonstrated by the purely terrestrial δD values in the veins of Nakhla 110, a thin-section exposed to the terrestrial atmosphere since its preparation in 1998. Mineralogical heterogeneity also affects the hydrogen isotope exchange rate in these veins - the wide variation in δD within the veins of Nakhla and Y 000593 appears to be due to the heterogeneous nature of the vein material, where some phases exchange hydrogen with the atmosphere at a faster rate than others.

  8. Interaction of hydrogen chloride with alumina. [influence of outgas and temperature conditions on adsorption

    NASA Technical Reports Server (NTRS)

    Bailey, R. R.; Wightman, J. P.

    1975-01-01

    The influence of outgas conditions and temperature on the adsorptive properties of two aluminas Alon-c and Al6sG were studied using adsorption isotherm measurements. Alon-C and Al6SG were characterized using X-ray powder diffraction, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and BET nitrogen surface areas. Some of these techniques were applied to two other aluminas but no isotherm data was obtained. Isotherm data and techniques applied to each alumina are summarized in tabular form.

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

    NASA Astrophysics Data System (ADS)

    Wolhowe, M. D.; Prahl, F. G.; Probert, I.; Maldonado, M.

    2009-08-01

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

  10. Characterization of narrow micropores in almond shell biochars by nitrogen, carbon dioxide, and hydrogen adsorption

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Characterization of biochars usually includes surface area and pore volume determination by nitrogen adsorption. In this study, we show that there is a substantial pore volume in biochars created via slow pyrolysis from low- and high-ash almond shells that cannot be characterized in this fashion due...

  11. Stable hydrogen-isotope ratios in beetle chitin: preliminary European data and re-interpretation of North American data

    NASA Astrophysics Data System (ADS)

    Gröcke, Darren R.; Schimmelmann, Arndt; Elias, Scott; Miller, Randall F.

    2006-08-01

    Beetle exoskeletons contain chitin, a poly amino-sugar that is biosynthesized incorporating hydrogen isotopes from diet and water. As the stable isotope ratios D/H (or 2H/ 1H, expressed as δ D values) of precipitation and diet are jointly influenced by climate, the biochemically recorded hydrogen-isotope ratio in fossil beetle exoskeleton has the potential to be used for paleoclimatic reconstruction. New δ D data from modern beetles are presented as a preliminary database for Europe, with a re-evaluation of earlier North American data. We present correlated matrices of δ D values in modern beetle chitin and modern precipitation to demonstrate the concept. We review the pertinent literature to highlight the history, utility, and likely future research directions for the use of chitin's stable isotopes in entomological paleoclimatology.

  12. The fractionation factors of stable carbon and hydrogen isotope ratios for VOCs

    NASA Astrophysics Data System (ADS)

    Kawashima, H.

    2014-12-01

    Volatile organic compounds (VOCs) are important precursors of ozone and secondary organic aerosols in the atmosphere, some of which are carcinogenic, teratogenic, or mutagenic. VOCs in ambient air originate from many sources, including vehicle exhausts, gasoline evaporation, solvent use, natural gas emissions, and industrial processes, and undergo intricate chemical reactions in the atmosphere. To develop efficient air pollution remediation strategies, it is important to clearly identify the emission sources and elucidate the reaction mechanisms in the atmosphere. Recently, stable carbon isotope ratios (δ13C) of VOCs in some sources and ambient air have been measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In this study, we measured δ13C and stable hydrogen isotope ratios (δD) of atmospheric VOCs by using the gas chromatography/thermal conversion/isotope ratio mass spectrometry coupled with a thermal desorption instrument (TD-GC/TC/IRMS). The wider δD differences between sources were found in comparison with the δ13C studies. Therefore, determining δD values of VOCs in ambient air is potentially useful in identifying VOC sources and their reactive behavior in the atmosphere. However, to elucidate the sources and behavior of atmospheric VOCs more accurately, isotopic fractionation during atmospheric reaction must be considered. In this study, we determined isotopic fractionation of the δ13C and δD values for the atmospheric some VOCs under irradiation conditions. As the results, δ13C for target all VOCs and δD for most VOCs were increasing after irradiation. But, the δD values for both benzene and toluene tended to decrease as irradiation time increased. We also estimated the fractionation factors for benzene and toluene, 1.27 and 1.05, respectively, which differed from values determined in previous studies. In summary, we were able to identify an inverse isotope effect for the δD values of benzene and toluene

  13. Isotopic fractionation of hydrogen in planetary exospheres due to ionosphere-exosphere coupling - Implications for Venus

    NASA Astrophysics Data System (ADS)

    Hodges, R. R.

    1993-06-01

    The paper considers isotopic hydrogen fractionation processes in the Venusian exosphere due to ionosphere-exosphere coupling by addressing two deficiencies in the present theory of differential escape. First, a set of D/H isotopic fractionation curves is derived for the ion-neutral interactions of charge and collisional momentum transfer, and these are compared with the results of Gurwell and Yung (1993) for hot O collisional ejection. Then, the question of the relative importance of collisional ejection in atmospheric escape is reexamined using two simple exosphere models. It is shown that O-O collisions suppress the high energy component of the hot O distribution by more than a factor of 10. Moreover, the ballistic trajectories of fast O atoms that reach the nighttime reservoir of exospheric hydrogen favor downward scatter of D and H rather than their escape. It is concluded that, due to severe limits placed on the effectiveness of collisional ejection, the differential escape of D and H from Venus is determined by charge exchange interactions rather than the collisional ejection.

  14. Isotopic fractionation of hydrogen in planetary exospheres due to ionosphere-exosphere coupling - Implications for Venus

    NASA Technical Reports Server (NTRS)

    Hodges, R. R., Jr.

    1993-01-01

    The paper considers isotopic hydrogen fractionation processes in the Venusian exosphere due to ionosphere-exosphere coupling by addressing two deficiencies in the present theory of differential escape. First, a set of D/H isotopic fractionation curves is derived for the ion-neutral interactions of charge and collisional momentum transfer, and these are compared with the results of Gurwell and Yung (1993) for hot O collisional ejection. Then, the question of the relative importance of collisional ejection in atmospheric escape is reexamined using two simple exosphere models. It is shown that O-O collisions suppress the high energy component of the hot O distribution by more than a factor of 10. Moreover, the ballistic trajectories of fast O atoms that reach the nighttime reservoir of exospheric hydrogen favor downward scatter of D and H rather than their escape. It is concluded that, due to severe limits placed on the effectiveness of collisional ejection, the differential escape of D and H from Venus is determined by charge exchange interactions rather than the collisional ejection.

  15. Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution: Possibly a Termolecular Liquid Phase Reaction.

    PubMed

    Gabričević, Mario; Lente, Gábor; Fábián, István

    2015-12-24

    This work reports an experimental study of the hydrogen/deuterium exchange in the basic aqueous solutions of trichloroethylene, trans-1,2-dichloroethylene, and cis-1,2-dichloroethylene using (1)H NMR as a monitoring method. 1,1-Dichlorethylene was also investigated but found not to exchange hydrogen isotopes with water. The kinetics of isotope exchange features two different pathways, the first is first order with respect to hydroxide ion, whereas the second is second order. The first pathway is interpreted as a straightforward bimolecular reaction between chloroethylene and hydroxide ion, which leads to the deprotonation of chloroethylene. The second pathway involves a transition state with the association of one molecule of the chloroethylene and two hydroxide ions. It is shown that the second pathway could involve the formation of a precursor complex composed of one chloroethylene molecule and one hydroxide ion, but a direct termolecular elementary reaction is also feasible, which is shown by deriving a theoretical highest limit for the rate constants of termolecular reactions in solution. PMID:26618984

  16. Impact of metabolism and growth phase on the hydrogen isotopic composition of microbial fatty acids

    PubMed Central

    Heinzelmann, Sandra M.; Villanueva, Laura; Sinke-Schoen, Danielle; Sinninghe Damsté, Jaap S.; Schouten, Stefan; van der Meer, Marcel T. J.

    2015-01-01

    Microorganisms are involved in all elemental cycles and therefore it is important to study their metabolism in the natural environment. A recent technique to investigate this is the hydrogen isotopic composition of microbial fatty acids, i.e., heterotrophic microorganisms produce fatty acids enriched in deuterium (D) while photoautotrophic and chemoautotrophic microorganisms produce fatty acids depleted in D compared to the water in the culture medium (growth water). However, the impact of factors other than metabolism have not been investigated. Here, we evaluate the impact of growth phase compared to metabolism on the hydrogen isotopic composition of fatty acids of different environmentally relevant microorganisms with heterotrophic, photoautotrophic and chemoautotrophic metabolisms. Fatty acids produced by heterotrophs are enriched in D compared to growth water with εlipid/water between 82 and 359‰ when grown on glucose or acetate, respectively. Photoautotrophs (εlipid/water between −149 and −264‰) and chemoautotrophs (εlipid/water between −217 and −275‰) produce fatty acids depleted in D. Fatty acids become, in general, enriched by between 4 and 46‰ with growth phase which is minor compared to the influence of metabolisms. Therefore, the D/H ratio of fatty acids is a promising tool to investigate community metabolisms in nature. PMID:26005437

  17. Involvement of Pore Fluids During Frictional Melting from Hydrogen Isotopic Investigation of Pseudotachylytes

    NASA Astrophysics Data System (ADS)

    Dallai, L.; Mittempergher, S.; di Toro, G.; Pennacchioni, G.

    2008-12-01

    Pseudotachylytes are frictional melts produced during seismic slip and solidified in short time (seconds to minutes) after an earthquake. We investigated the presence and role of hydrous fluids during seismic faulting by measuring the Deuterium/Hydrogen (D/H) ratios (δD) in natural and artificial pseudotachylytes and in their host rocks. Pseudotachylytes from faults of the Adamello (Italian Alps) formed at 9-11 km depth and 250-300°C are hosted in tonalite (hydrated phase is biotite) and cataclasite (hydrated minerals are epidote and minor chlorite). The δD values range from -73 ± 2 ‰ for tonalite (i.e., biotite) to -64 ± 4 ‰ for cataclasite (epidote+chlorite). Artificial pseudotachylytes were obtained from tonalites and cataclasites in friction experiments simulating seismic slip under dry conditions. Dehydration of biotite in tonalite and epidote+chlorite in cataclasite provided the source for water in pseudotachylytes. Artificial pseudotachylyte δD values range from -75 ± 1‰ for samples produced from tonalite to - 83 ± 2‰ for samples involving cataclasite. Instead, natural pseudotachylytes have more negative δD values ranging between -103.6 and -83.4‰, irrespective of wall rock composition and pseudotachylyte thickness. In experimental pseudotachylytes, SEM analysis suggests that the negative δD shift of pseudotachylytes produced from cataclasites resulted from hydrogen fractionation during partial melting of epidote (melting point 1050°C) in the wall rocks; differently, total melting of biotite (due to its lower melting temperature of 650°C) and rapid cooling allowed negligible H-isotope fractionation between biotite and pseudotachylite. In natural pseudotachylytes, microstructural and geochemical observations rule out (i) meteoric alteration of the pseudotachylyte by isotopically light water and, (ii) isotope re-equilibration between acqueous fluid and matrix minerals during pseudotachylyte cooling to ambient temperature (devitrification

  18. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2011-12-01

    Biologically produced molecular hydrogen (H2) is characterized by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of molecular hydrogen (H2). Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. We investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production, and from several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δD = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δDH2O = 73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰). The pure culture samples from different microorganisms give a mean source signature of δD = -728‰ (±39‰), and a fractionation constant ϵH2-H2O of -711‰ (±45‰) between H2 and the water, respectively. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapor. As expected for a thermodynamic equilibrium, the fractionation factor is largely independent of the substrates used and the H2 production conditions. The predicted equilibrium fractionation coefficient is positively correlated with temperature and we measured a change of 2.2‰/°C between 45 °C and 60 °C. This is in general agreement with the theoretical predictions. Our

  19. Isotope Dependence and Quantum Effects on Atomic Hydrogen Diffusion in Liquid Water.

    PubMed

    Walker, J A; Mezyk, S P; Roduner, E; Bartels, D M

    2016-03-01

    Relative diffusion coefficients were determined in water for the D, H, and Mu isotopes of atomic hydrogen by measuring their diffusion-limited spin-exchange rate constants with Ni(2+) as a function of temperature. H and D atoms were generated by pulse radiolysis of water and measured by time-resolved pulsed EPR. Mu atoms are detected by muonium spin resonance. To isolate the atomic mass effect from solvent isotope effect, we measured all three spin-exchange rates in 90% D2O. The diffusion depends on the atomic mass, demonstrating breakdown of Stokes-Einstein behavior. The diffusion can be understood using a combination of water "cavity diffusion" and "hopping" mechanisms, as has been proposed in the literature. The H/D isotope effect agrees with previous modeling using ring polymer molecular dynamics. The "quantum swelling" effect on muonium due to its larger de Broglie wavelength does not seem to slow its "hopping" diffusion as much as predicted in previous work. Quantum effects of both the atom mass and the water librations have been modeled using RPMD and a qTIP4P/f quantized flexible water model. These results suggest that the muonium diffusion is very sensitive to the Mu versus water potential used. PMID:26623663

  20. Hydrogen-isotopic variability in fatty acids from Yellowstone National Park hot spring microbial communities

    NASA Astrophysics Data System (ADS)

    Osburn, Magdalena R.; Sessions, Alex L.; Pepe-Ranney, Charles; Spear, John R.

    2011-09-01

    We report the abundances and hydrogen-isotopic compositions (D/H ratios) of fatty acids extracted from hot-spring microbial mats in Yellowstone National Park. The terrestrial hydrothermal environment provides a useful system for studying D/H fractionations because the numerous microbial communities in and around the springs are visually distinct, separable, and less complex than those in many other aquatic environments. D/H fractionations between lipids and water ranged from -374‰ to +41‰ and showed systematic variations between different types of microbial communities. Lipids produced by chemoautotrophic hyperthermophilic bacteria, such as icosenoic acid (20:1), generally exhibited the largest and most variable fractionations from water (-374‰ to -165‰). This was in contrast to lipids characteristic of heterotrophs, such as branched, odd chain-length fatty acids, which had the smallest fractionations (-163‰ to +41‰). Mats dominated by photoautotrophs exhibited intermediate fractionations similar in magnitude to those expressed by higher plants. These data support the hypothesis that variations in lipid D/H are strongly influenced by central metabolic pathways. Shifts in the isotopic compositions of individual fatty acids across known ecological boundaries show that the isotopic signature of specific metabolisms can be recognized in modern environmental samples, and potentially recorded in ancient ones. Considering all sampled springs, the total range in D/H ratios is similar to that observed in marine sediments, suggesting that the trends observed here are not exclusive to the hydrothermal environment.

  1. Authenticity and traceability of vanilla flavors by analysis of stable isotopes of carbon and hydrogen.

    PubMed

    Hansen, Anne-Mette Sølvbjerg; Fromberg, Arvid; Frandsen, Henrik Lauritz

    2014-10-22

    Authenticity and traceability of vanilla flavors were investigated using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). Vanilla flavors produced by chemical synthesis (n = 2), fermentation (n = 1), and extracted from two different species of the vanilla orchid (n = 79) were analyzed. The authenticity of the flavor compound vanillin was evaluated on the basis of measurements of ratios of carbon stable isotopes (δ(13)C). It was found that results of δ(13)C for vanillin extracted from Vanilla planifolia and Vanilla tahitensis were significantly different (t test) and that it was possible to differentiate these two groups of natural vanillin from vanillin produced otherwise. Vanilla flavors were also analyzed for ratios of hydrogen stable isotopes (δ(2)H). A graphic representation of δ(13)C versus δ(2)H revealed that vanillin extracted from pods grown in adjacent geographic origins grouped together. Accordingly, values of δ(13)C and δ(2)H can be used for studies of authenticity and traceability of vanilla flavors. PMID:25266169

  2. Fabrication of Low Adsorption Energy Ni-Mo Cluster Cocatalyst in Metal-Organic Frameworks for Visible Photocatalytic Hydrogen Evolution.

    PubMed

    Zhen, Wenlong; Gao, Haibo; Tian, Bin; Ma, Jiantai; Lu, Gongxuan

    2016-05-01

    An effective cocatalyst is crucial for enhancing the visible photocatalytic performance of the hydrogen generation reaction. By using density-functional theory (DFT) and frontier molecular orbital (FMO) theory calculation analysis, the hydrogen adsorption free energy (ΔGH) of Ni-Mo alloy (458 kJ·mol(-1)) is found to be lower than that of Ni itself (537 kJ·mol(-1)). Inspired by these results, the novel, highly efficient cocatalyst NiMo@MIL-101 for photocatalysis of the hydrogen evolution reaction (HER) was fabricated using the double solvents method (DSM). In contrast with Ni@MIL-101 and Mo@MIL-101, NiMo@MIL-101 exhibited an excellent photocatalytic performance (740.2 μmol·h(-1) for HER), stability, and high apparent quantum efficiency (75.7%) under 520 nm illumination at pH 7. The NiMo@MIL-101 catalyst also showed a higher transient photocurrent, lower overpotential (-0.51 V), and longer fluorescence lifetime (1.57 ns). The results uncover the dependence of the photocatalytic activity of HER on the ΔGH of Ni-Mo (MoNi4) alloy nanoclusters, i.e., lower ΔGH corresponding to higher HER activity for the first time. The NiMo@MIL-101 catalyst could be a promising candidate to replace precious-metal catalysts of the HER. PMID:27070204

  3. Biochemical hydrogen isotope fractionation during biosynthesis in higher plants reflects carbon metabolism of the plant

    NASA Astrophysics Data System (ADS)

    Cormier, Marc-André; Kahmen, Ansgar

    2015-04-01

    Compound-specific isotope analyses of plant material are frequently applied to understand the response of plants to the environmental changes. As it is generally assume that the main factors controlling δ2H values in plants are the plant's source water and evaporative deuterium enrichment of leaf water, hydrogen isotope analyses of plant material are mainly applied regarding hydrological conditions at different time scales. However, only few studies have directly addressed the variability of the biochemical hydrogen isotope fractionation occurring during biosynthesis of organic compounds (ɛbio), accounting also for a large part in the δ2H values of plants but generally assumed to be constant. Here we present the results from a climate-controlled growth chambers experiment where tested the sensitivity of ɛbio to different light treatments. The different light treatments were applied to induce different metabolic status (autotrophic vs. heterotrophic) in 9 different plant species that we grew from large storage organs (e.g. tubers or roots). The results show a systematic ɛbio shift (up to 80 ) between the different light treatments for different compounds (i.e. long chain n-alkanes and cellulose). We suggest that this shift is due to the different NADPH pools used by the plants to build up the compounds from stored carbohydrates in heterotrophic or autotrophic conditions. Our results have important implications for the calibration and interpretation of sedimentary and tree rings records in geological studies. In addition, as the δ2H values reflect also strongly the carbon metabolism of the plant, our findings support the idea of δ2H values as an interesting proxy for plant physiological studies.

  4. Geochemistry and origin of formation waters in the western Canada sedimentary basin-I. Stable isotopes of hydrogen and oxygen

    USGS Publications Warehouse

    Hitchon, B.; Friedman, I.

    1969-01-01

    Stable isotopes of hydrogen and oxygen, together with chemical analyses, were determined for 20 surface waters, 8 shallow potable formation waters, and 79 formation waters from oil fields and gas fields. The observed isotope ratios can be explained by mixing of surface water and diagenetically modified sea water, accompanied by a process which enriches the heavy oxygen isotope. Mass balances for deuterium and total dissolved solids in the western Canada sedimentary basin demonstrate that the present distribution of deuterium in formation waters of the basin can be derived through mixing of the diagenetically modified sea water with not more than 2.9 times as much fresh water at the same latitude, and that the movement of fresh water through the basin has redistributed the dissolved solids of the modified sea water into the observed salinity variations. Statistical analysis of the isotope data indicates that although exchange of deuterium between water and hydrogen sulphide takes place within the basin, the effect is minimized because of an insignificant mass of hydrogen sulphide compared to the mass of formation water. Conversely, exchange of oxygen isotopes between water and carbonate minerals causes a major oxygen-18 enrichment of formation waters, depending on the relative masses of water and carbonate. Qualitative evidence confirms the isotopic fractionation of deuterium on passage of water through micropores in shales. ?? 1969.

  5. Emissions of molecular hydrogen (H2) and its isotopic signature from residential heaters and waste incinerators

    NASA Astrophysics Data System (ADS)

    Vollmer, M. K.; Walter, S.; Mohn, J.; Steinbacher, M.; Bond, S. W.; Roeckmann, T.; Reimann, S.

    2011-12-01

    Atmospheric molecular hydrogen (H2) has recently received increased interest in the scientific community because of a potential shift to a global hydrogen energy economy which could potentially alter the atmospheric budget of H2 due to substantial leakage. This calls for an improved understanding of the present day's atmospheric H2 budget. One of the major sources of H2 are emissions from incomplete combustion of fossil fuel. While emissions of H2 from car exhaust have been studied extensively, those from fossil fuel based heating systems have remained a matter of speculation. Here we present results from measurements of a variety of residential heating systems covering oil, gas, and wood heating with various burner capacities. For oil and gas heating systems we surprisingly find no net H2 emissions, i.e. the exhaust air contains H2 at or below the mole fractions of the intake air (approx. 0.5 ppm). While H2 emissions are virtually absent, those of carbon monoxide (CO) are not. As a consequence, caution has to be exercised when modeling H2 emissions based on assumed H2/CO ratios and using CO emission inventories. We also find that the molecular hydrogen in the approx. 0.5 ppm exhaust air is isotopically strongly depleted (-20 permil to -200 permil) compared to the ambient air (+130 permil). This suggests that H2 is involved in the combustion processes, and therefore the H2 of the intake air is not the same H2 in the exhaust air. Exhausts from waste incinerator plants are generally also depleted in H2 mole fractions and in their H/D isotopic composition.

  6. Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers

    NASA Astrophysics Data System (ADS)

    Purewal, J. J.; Kabbour, H.; Vajo, J. J.; Ahn, C. C.; Fultz, B.

    2009-05-01

    Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.

  7. Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers.

    PubMed

    Purewal, J J; Kabbour, H; Vajo, J J; Ahn, C C; Fultz, B

    2009-05-20

    Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference. PMID:19420660

  8. Correlation between hydrogen isotope ratios of lipid biomarkers and sediment maturity

    NASA Astrophysics Data System (ADS)

    Radke, Jens; Bechtel, Achim; Gaupp, Reinhard; Püttmann, Wilhelm; Schwark, Lorenz; Sachse, Dirk; Gleixner, Gerd

    2005-12-01

    We investigated the influence of thermal maturity on the hydrogen isotope ratios of sedimentary hydrocarbons to prove that the isotope ratio of hydrocarbons mirrors paleoclimate signatures. δD values from n-alkanes and acyclic isoprenoids of two sediment sections (Kupferschiefer [KS], 258 Ma, and Posidonienschiefer [PS], 184 Ma) with different maturation history were investigated. Both covered thermal maturity from 0.48 to 1.3 Rc (vitrinite reflectance and reflectance calculated from MPI1). Sediment burial up to 4500 m caused thermal maturation of organic matter in the KS horizon from the Early Zechstein basin of Poland, whereas contact metamorphic thermal maturation originated in the Early Toarcian PS (Posidonienschiefer) of the North German Vlotho Massif. The δD values of the extracted n-alkanes positively correlate with thermal maturity in the KS ( y = 56‰ × MPI1[ x] - 160‰ [VSMOW]) and in the PS ( y = 104‰ × MPI1[ x] - 200‰ [VSMOW]). The δD values of isoprenoids (i.e., pristane, phytane) were even more enriched with increasing maturity ( y = 179‰ × MPI1[ x] - 341‰ [VSMOW] in the KS; y = 300‰ × MPI1[ x] - 415‰ [VSMOW] in PS). These results explain why isotope ratios of n-alkanes and isoprenoids in mature sediments are generally enriched in D and do not have the expected isotopic difference between n-alkanes and isoprenoids of ˜190‰. Moreover, the correlation between sediment maturity parameters and δD values suggests that after correction the δD values of n-alkanes can be used to reconstruct climate and environment in the geological past.

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

    USGS Publications Warehouse

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

    2005-01-01

    The Trinity peridotite represents a rare opportunity to examine a relatively fertile plagioclase peridotite that was exhumed and later subjected to intrusive events in a seafloor environment, followed by its emplacement and incorporation into a continent. Over 250 stable isotopic determinations on whole rocks and minerals elucidate the hydrothermal evolution of the Trinity complex. All three serpentine polymorphs are present in the Trinity peridotite; these separate on the basis of their ??D values: antigorite, -46 < ??D < -82??? and lizardite and chrysotile, -90 < ??D < -106 and -110 < ??D < -136???, respectively. Antigorite coexists with chlorite, talc, and tremolite in contact aureole assemblages associated with Silurian/Devonian gabbroic plutons. Lizardite and chrysotile alteration carries a meteoric signature, which suggests association with post-emplacement serpentinization, or overprinting of earlier low-temperature seafloor serpentinization. Regionally, contours of ??D values exhibit bull's-eye patterns associated with the gabbroic plutons, with ??D maxima coinciding with the blackwall alteration at the margins on the plutons. In contrast to the hydrogen isotope behavior, oxygen isotope values of the three polymorphs are indistinguishable, spanning the range 5.3 < ??18O< 7.5, and suggesting low integrated fluid fluxes and strongly 18O-shifted fluids. Inferred primary ?? 18O values for peridotite, gabbro, and late Mesozoic granodiorite indicate a progressive 18O enrichment with time for the source regions of the rocks. These isotopic signatures are consistent with the geology, petrochemistry, and geochronology of the Trinity massif, which indicate the following history: (1) lithospheric emplacement and cooling of the peridotite in an oceanic environment ??? 472 Ma; (2) intrusion of gabbroic plutons into cold peridotite in an arc environment between 435 and 404 Ma; and finally (3) intrusion of felsic plutons between 171 and 127 Ma, long after the peridotite

  10. MEASUREMENT OF THE ISOTOPIC COMPOSITION OF HYDROGEN AND HELIUM NUCLEI IN COSMIC RAYS WITH THE PAMELA EXPERIMENT

    SciTech Connect

    Adriani, O.; Bongi, M.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Bruno, A.; Boezio, M.; Bonvicini, V.; Carbone, R.; Bogomolov, E. A.; Borisov, S.; Casolino, M.; De Pascale, M. P.; Bottai, S.; Cafagna, F.; Campana, D.; Carlson, P.; Castellini, G.; Danilchenko, I. A.; De Santis, C.; and others

    2013-06-10

    The satellite-borne experiment PAMELA has been used to make new measurements of cosmic ray H and He isotopes. The isotopic composition was measured between 100 and 600 MeV/n for hydrogen and between 100 and 900 MeV/n for helium isotopes over the 23rd solar minimum from 2006 July to 2007 December. The energy spectrum of these components carries fundamental information regarding the propagation of cosmic rays in the galaxy which are competitive with those obtained from other secondary to primary measurements such as B/C.

  11. Ab initio calculations for dissociative hydrogen adsorption on lithium oxide surfaces

    SciTech Connect

    Sutjianto, A. |; Tam, S.W.; Curtiss, L.A.; Johnson, C.E.; Pandey, R.

    1994-12-01

    Lithium ceramics are one class of materials being considered as tritium breeders for fusion technology,and hydrogen is known to enhance the release of tritium from lithium ceramic materials. Dissociative hydrogen chemisorption on the Li{sub 2}O surfaces of the (100), (110), and (111) planes has been investigated with ab initio Hartree-Fock calculations. Calculations for unrelaxed crystal Li{sub 2}O structures indicated that except for the (100) surface, the (110) and (111) surfaces are stable. Results on the heterolytic sites of n-layer (110) (where n {ge} 2) slabs and three-layer (111) slabs suggest that dissociative hydrogen chemisorption is endothermic. For a one-layer (110) slab at 100% surface coverage, the dissociative hydrogen chemisorption is exothermic, forming OH{sup {minus}} and Li{sup +}H{sup {minus}}Li{sup +}. The results also indicate that the low coordination environment in surface step structures, such as kinks and ledges, may plan an important role in the hydrogen chemisorption process. On the homolytic sites of the (110) and (111) surfaces, there is no hydrogen chemisorption.

  12. Defect formation on the GaSb (001) surface induced by hydrogen atom adsorption

    NASA Astrophysics Data System (ADS)

    Bermudez, V. M.

    2015-06-01

    Density functional theory has been used to characterize the effects of adsorbed H on the electronic structure of the GaSb (001)-α(4×3) surface, which consists of a combination of Ga-Sb and Sb-Sb dimers. Adsorption of two H atoms at a Ga-Sb adatom dimer either has little effect on surface states above the bulk valence band maximum (VBM) or else eliminates them, depending on the mode of adsorption. However, adsorption at the Sb-Sb dimer in the terminating layer produces a state farther into the gap at ~0.10 eV above the clean-surface VBM. Relaxation accompanying the breaking of the Sb-Sb dimer bond leads to increased interactions involving three-fold-coordinated Sb sites in the terminating layer, which in turn raises the energies of the non-bonding lone-pair orbitals. This defect state, which appears to be unique to the reconstructed GaSb (001) surface, could potentially function as a hole trap on the surface of p-type GaSb.

  13. Adsorptive capacity and evolution of the pore structure of alumina on reaction with gaseous hydrogen fluoride.

    PubMed

    McIntosh, Grant J; Agbenyegah, Gordon E K; Hyland, Margaret M; Metson, James B

    2015-05-19

    Brunauer-Emmet-Teller (BET) specific surface areas are generally used to gauge the propensity of uptake on adsorbents, with less attention paid to kinetic considerations. We explore the importance of such parameters by modeling the pore size distributions of smelter grade aluminas following HF adsorption, an industrially important process in gas cleaning at aluminum smelters. The pore size distributions of industrially fluorinated aluminas, and those contacted with HF in controlled laboratory trials, are reconstructed from the pore structure of the untreated materials when filtered through different models of adsorption. These studies demonstrate the presence of three distinct families of pores: those with uninhibited HF uptake, kinetically limited porosity, and pores that are surface blocked after negligible scrubbing. The surface areas of the inaccessible and blocked pores will overinflate estimates of the adsorption capacity of the adsorbate. We also demonstrate, contrary to conventional understanding, that porosity changes are attributed not to monolayer uptake but more reasonably to pore length attenuation. The model assumes nothing specific regarding the Al2O3-HF system and is therefore likely general to adsorbate/adsorbent phenomena. PMID:25913681

  14. Adsorption of alcohols and fatty acids onto hydrogenated (a-C:H) DLC coatings

    NASA Astrophysics Data System (ADS)

    Simič, R.; Kalin, M.; Kovač, J.; Jakša, G.

    2016-02-01

    Information about the interactions between lubricants and DLC coatings is scarce, despite there having been many studies over the years. In this investigation we used ToF-SIMS, XPS and contact-angle analyses to examine the adsorption ability and mechanisms with respect to two oiliness additives, i.e., hexadecanol and hexadecanoic acid, on an a-C:H coating. In addition, we analyzed the resistance of the adsorbed films to external influences like solvent cleaning. The results show that both molecules adsorb onto surface oxides and hydroxides present on the initial DLC surface and shield these structures with their hydrocarbon tails. This makes the surfaces less polar, which is manifested in a smaller polar component of the surface energy. We also showed that ultrasonic cleaning in heptane has no significant effect on the quantity of adsorbed molecules or on their chemical state. This not only shows the relatively strong adsorption of these molecules, but also provides useful information for future experimental work. Of the two examined molecules, the acid showed a greater adsorption ability than the alcohol, which explains some of the previously reported better tribological properties in the case of the acid with respect to the alcohol.

  15. Wetting Camphor: Multi-Isotopic Substitution Identifies the Complementary Roles of Hydrogen Bonding and Dispersive Forces.

    PubMed

    Pérez, Cristóbal; Krin, Anna; Steber, Amanda L; López, Juan C; Kisiel, Zbigniew; Schnell, Melanie

    2016-01-01

    Using broadband rotational spectroscopy, we report here on the delicate interplay between hydrogen bonds and dispersive forces when an unprecedentedly large organic molecule (camphor, C10H16O) is microsolvated with up to three molecules of water. Unambiguous assignment was achieved by performing multi H2(18)O isotopic substitution of clustered water molecules. The observation of all possible mono- and multi-H2(18)O insertions in the cluster structure yielded accurate structural information that is not otherwise achievable with single-substitution experiments. The observed clusters exhibit water chains starting with a strong hydrogen bond to the C═O group and terminated by a mainly van der Waals (dispersive) contact to one of the available sites at the monomer moiety. The effect of hydrogen bond cooperativity is noticeable, and the O···O distances between the clustered water subunits decrease with the number of attached water molecules. The results reported here will further contribute to reveal the hydrophobic and hydrophilic interactions in systems of increasing size. PMID:26689110

  16. Theoretical study of hydrogen adsorption on Ca-decorated C{sub 48}B{sub 12} clusters

    SciTech Connect

    Qi, Pengtang; Chen, Hongshan

    2015-09-15

    The hydrogen adsorption on Ca-decorated C{sub 48}B{sub 12} clusters is studied using density functional theory. The favorable binding site for Ca atom is the hexagonal C{sub 4}B{sub 2} rings. The strong interaction between Ca atoms and C{sub 48}B{sub 12} cluster hinders the aggregation of Ca atoms on the cluster surface. C{sub 48}B{sub 12} is an electron deficient system with a large electron affinity of 2.952 eV. The decorated Ca atoms transfer their electrons to the cluster easily. The net charges on the Ca atoms are in the range of 1.101 to 1.563 e. When H{sub 2} molecules approach the Ca atoms, they are moderately polarized and adsorbed around the Ca atoms in molecular form. The adsorption strength can reach up to 0.133 eV/H{sub 2}. Each Ca atom in the Ca-decorated C{sub 48}B{sub 12} complexes can adsorb three H{sub 2} molecules. The fully decorated C{sub 48}B{sub 12}Ca{sub 6} can hold up to 18 H{sub 2} molecules.

  17. The atomic coilgun and single-photon cooling. A method for trapping and cooling of hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Libson, Adam; Bannerman, Stephen Travis; Clark, Robert J.; Mazur, Thomas R.; Raizen, Mark G.

    2012-12-01

    As the simplest atom, hydrogen has a unique role as a testing ground of fundamental physics. Precision measurements of the hydrogen atomic structure provide stringent tests of current theory, while tritium is an excellent candidate for studies of β-decay and possible measurement of the neutrino rest mass. Furthermore, precision measurement of antihydrogen would allow for tests of fundamental symmetries. Methods demonstrated in our lab provide an avenue by which hydrogen isotopes can be trapped and cooled to near the recoil limit. The atomic coilgun, which we have demonstrated with metastable neon and molecular oxygen, provides a general method of stopping a supersonic beam of any paramagnetic species. This tool provides a method by which hydrogen and its isotopes can be magnetically trapped at around 100 mK using a room temperature apparatus. Another tool developed in our laboratory, single-photon cooling, allows further cooling of a trapped sample to near the recoil limit. This cooling method has already been demonstrated on a trapped sample of rubidium. We report on the progress of implementing these methods to trap and cool hydrogen isotopes, and on the prospects for using cold trapped hydrogen for precision measurements.

  18. Carbon and hydrogen isotope effects in the open-system Fischer-Tropsch type reactions. Implications for abiogenic hydrocarbons in the Earth Crust

    NASA Astrophysics Data System (ADS)

    Taran, Y.

    2009-05-01

    This study aims to clarify the isotope effects in the open-system Fischer-Tropsh type (FTT) synthesis with application to the problem of 'abiogenic' hydrocarbons. Carbon and hydrogen isotopic compositions were measured for products of catalytic hydrogenation of CO2 on cobalt and iron catalysts at 245° C and 350° C and 10 MPa in a flow-through reactor. No carbon isotope fractionation between methane and longer hydrocarbons was observed, independently on the CO2 conversion. The hydrogen isotope fractionation appeared to be similar to that found in natural ('thermogenic' and 'biogenic') gases with the enrichment in deuterium of longer hydrocarbon chains and the higher effects for the Co-catalyst. It can be suggested that other than FTT reactions or a simple mixing are responsible for the occurrence of 'inverse' isotopic trends in both carbon and hydrogen isotopic composition found in light hydrocarbons in some specific terrestrial environments and meteorites.

  19. Hydrogen Isotopic Composition of Particulate-Bound Fatty Acids From the California Borderland Basins

    NASA Astrophysics Data System (ADS)

    Jones, A. A.; Sessions, A. L.; Campbell, B. J.; Valentine, D. L.

    2006-12-01

    We examined the hydrogen-isotopic composition of fatty acids associated with particulate organic matter (POM) from depth transects in three California Borderland stations. Our goals were to determine (1) the natural variability of δD values in POM-associated fatty acids and (2) the magnitude of isotopic fractionations associated with fatty acid degradation in the marine environment. Some differences in molecular abundance were observed between completely ventilated and occasionally suboxic sites, but no corresponding shifts in δD values were measured. Values of δD for specific fatty acids were generally consistent between stations. Saturated fatty acids (C14, C16, and C18) yielded δD values ranging from -230‰ to -132‰, with δD values generally decreasing with chain length. We found no evidence of extreme D-enrichment of the C18 fatty acid as has been observed in studies of isolated macroalgae (Chikaraishi, et al, 2004). The unsaturated C16 and C18 fatty acids showed a similar trend while the polyunsaturated fatty acid 22:6 was somewhat enriched in D (δD values ranging from -186‰ to -68‰) relative to 20:5 (-208‰ to -93‰). Unsaturated fatty acids tended to have more positive δD values than their saturated counterparts, opposite the trend observed in sediments from the same location. The bacterial fatty acid C15 showed even greater deuterium enrichment with δD values ranging from - 145‰ to -88‰. This offset can likely be attributed to differences in biosynthetic fractionation between bacteria and eukaryotes, to differences in hydrogen isotopic composition of the food sources of these organisms, or some combination of these two factors. Within the surface waters, fatty acids become enriched with depth by an average of 25‰. The C18:0 acid is a significant exception, becoming depleted by 48‰ over that same interval. Below 100 meters depth, all fatty acids tend to become slightly depleted in D with increasing depth. The difference in δD values

  20. Hydrogen adsorption and diffusion around Si(0 0 1)/Si(1 1 0) corners in nanostructures.

    PubMed

    Smith, Richard; Brázdová, Veronika; Bowler, David R

    2014-07-23

    While the diffusion of hydrogen on silicon surfaces has been relatively well characterized, both experimentally and theoretically, diffusion around corners between surfaces, as will be found on nanowires and nanostructures, has not been studied. Motivated by nanostructure fabrication by Patterned Atomic Layer Epitaxy, we present a density functional theory study of the diffusion of hydrogen around the edge formed by the orthogonal (0 0 1) and (1 1 0) surfaces in silicon. We find that the barrier from (0 0 1) to (1 1 0) is approximately 0.3 eV lower than from (1 1 0) to (0 0 1), and that it is comparable to diffusion between rows on a clean surface, with no significant effect on the hydrogen patterns at the growth temperatures used. PMID:24957137

  1. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Tanuwijaya, V. V.; Hidayat, N. N.; Agusta, M. K.; Dipojono, H. K.

    2015-09-01

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO3 sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  2. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    SciTech Connect

    Tanuwijaya, V. V.; Hidayat, N. N. Agusta, M. K. Dipojono, H. K.

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  3. Rhizon sampler alteration of deep ocean sediment interstitial water samples, as indicated by chloride concentration and oxygen and hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Miller, Madeline D.; Adkins, Jess F.; Hodell, David A.

    2014-06-01

    their potential to inform past ocean salinity, δ18O, and temperature, high-resolution depth profiles of interstitial water chloride concentration and hydrogen and oxygen isotopes exist in very few locations. One of the primary limitations to the recovery of these depth profiles is that traditional interstitial water sampling requires 5-10 cm whole rounds of the sediment core, which has the potential to interfere with stratigraphic continuity. The Rhizon sampler, a nondestructive tool developed for terrestrial sediment interstitial water extraction, has been proposed for efficient and nondestructive sampling of ocean sediment pore waters. However, there exists little documentation on the reliability and performance of Rhizon samplers in deep ocean sediments, particularly in regard to their effect on chloride concentration and oxygen and hydrogen isotopic measurements. We perform an intercomparison of chloride concentration and oxygen and hydrogen isotopic composition in samples taken using traditional squeezing versus those taken with Rhizon samplers. We find that samples taken with Rhizons have positive biases in both chloride concentration and stable isotopic ratios relative to those taken by squeezing water from sediments in a hydraulic press. The measured offsets between Rhizon and squeeze samples are consistent with a combination of absorption by and diffusive fractionation through the hydrophilic membrane of the Rhizon sampler. These results suggest caution is needed when using Rhizons for sampling interstitial waters in any research of processes that leave a small signal-to-noise ratio in dissolved concentrations or isotope ratios.

  4. An efficient method for isolating individual long-chain alkenones for compound-specific hydrogen isotope analysis.

    PubMed

    D'Andrea, William J; Liu, Zhonghui; Da Rosa Alexandre, Marcelo; Wattley, Sarah; Herbert, Timothy D; Huang, Yongsong

    2007-05-01

    Hydrogen isotope ratios (2H/H or D/H) of long-chain unsaturated ketones (alkenones) preserved in lake and marine sediments hold great promise for paleoclimate studies. However, compound-specific hydrogen isotope analysis of individual alkenones has not been possible due to chromatographic coelution of alkenones with the same carbon chain length but different numbers of double bonds. Published studies have only reported the deltaD values of the mixture of coeluting alkenones. We developed an efficient procedure to isolate individual alkenones based on double-bond numbers using silica gel impregnated with silver nitrate. The chromatographic procedure is simple, inexpensive, and highly reproducible, offers 87-100% sample recovery, and allows for the first time hydrogen isotopic measurement on individual alkenones. deltaD values of specific di-, tri- and tetraunsaturated C37 alkenones produced by an Emiliania huxleyi culture, as well as those isolated from Greenland lake sediments, differ consecutively by 43-65 per thousand. These findings suggest that alkenones with different numbers of carbon-carbon double bonds express significantly different deltaD values and that coelution of different alkenones may lead to erroneous source water deltaD reconstructions. Our alkenone isolation approach opens a new avenue for paleoclimate reconstructions using hydrogen isotope ratios of individual alkenones. PMID:17391004

  5. Density functional theory calculations of point defects and hydrogen isotopes in Li4SiO4

    NASA Astrophysics Data System (ADS)

    Xiang, Xiaogang; Zhu, Wenjun; Lu, Tiecheng; Gao, Tao; Shi, Yanli; Yang, Mao; Gong, Yichao; Yu, Xiaohe; Feng, Lan; Wei, Yongkai; Lu, Zhipeng

    2015-10-01

    The Li4SiO4 is a promising breeder material for future fusion reactors. Radiation induced vacancies and hydrogen isotope related impurities are the major types of point defects in this breeder material. In present study, various kinds of vacancies and hydrogen isotopes related point defects in Li4SiO4 are investigated through density functional theory (DFT) calculations. The band gap of Li4SiO4 is determined by UV-Vis diffuse reflectance spectroscopy experiments. Formation energies of all possible charge states of Li, Si and O vacancies are calculated using DFT methods. Formation energies of possible charge states of hydrogen isotopes substitution for Li and O are also calculated. We found that Li-vacancies will dominate among all vacancies in neutral charge state under radiation conditions and the O, Li, and Si vacancies (VO,VLi,VSi) are stable in charge states +2, -1, -4 for most of the range of Fermi level, respectively. The interstitial hydrogen isotopes (Hi) and substitutional HLi are stable in the charge states +1, 0 for most of the range of Fermi level, respectively. Moreover, substitutional HO are stable in +1 charge states. We also investigated the process of tritium recovery by discussing the interaction between interstitial H and Li-vacancy, O-vacancy, and found that HO + and HLi 0 are the most common H related defects during radiation process.

  6. Method and means of reducing erosion of components of plasma devices exposed to helium and hydrogen isotope radiation

    DOEpatents

    Kaminsky, Manfred S.; Das, Santosh K.; Rossing, Thomas D.

    1977-01-25

    Surfaces of components of plasma devices exposed to radiation by atoms or ions of helium or isotopes of hydrogen can be protected from damage due to blistering by shielding the surfaces with a structure formed by sintering a powder of aluminum or beryllium and its oxide or by coating the surfaces with such a sintered metal powder.

  7. H/D isotopic recognition mechanism in hydrogen-bonded crystals of 3-methylacetanilide and 4-methylacetanilide

    NASA Astrophysics Data System (ADS)

    Flakus, Henryk T.; Śmiszek-Lindert, Wioleta; Hachuła, Barbara; Michta, Anna

    2012-11-01

    Polarized IR spectra of 3- and 4-methylacetanilide as well as their deuterium derivative crystals were measured at 293 K and at 77 K by a transmission method. The obtained results were interpreted within the limits of the "strong-coupling" theory. This approach facilitated the understanding of the H/D isotopic, temperature and dichroic effects observed in the hydrogen bond IR spectra. The existence of H/D isotopic "self-organization" phenomenon, depending on the non-random distribution of protons and deuterons in the crystal lattices of isotopically diluted samples of a compound was ascertained. This effect resulted from the dynamical co-operative interactions involving the closely spaced hydrogen bonds, each belonging to a different chain of associated 3- and 4-methylacetanilide molecules. In the case of 4-methylacetanilide crystals weaker but non-negligible exciton coupling also involved adjacent hydrogen bonds in each molecular chain and the H/D isotopic "self-organization" mechanism concerned at least four hydrogen bonds from each unit cell. The source of these phenomena was ascribed to the molecular electronic properties determined by aromatic rings linked to nitrogen atoms of the amide fragments.

  8. RFNC-VNIIEF experience in development and operation of hydrogen isotopes gas-handling systems for basic research

    SciTech Connect

    Yukhimchuk, A. A.; Il'kaev, R. I.

    2008-07-15

    Application of hydrogen isotopes in different fields of fundamental physics obtained by RFNC-VNIIEF in the last decade are presented. Gas-handling systems for scientific experiments, some technologies and designs of the setup key elements are described, and results obtained with the developed equipment are outlined. (authors)

  9. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    PubMed

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. PMID:25877865

  10. Gas Feeding System Supplying the U-400M Cyclotron Ion Source with Hydrogen Isotopes

    SciTech Connect

    Yukhimchuk, A.A.; Angilopov, V.V.; Apasov, V.A.

    2005-07-15

    Automated system feeding into ion source hydrogen isotopes as molecules with preset ratio of the fluxes is described. The control system automatically maintained the working parameters and provided graphic and digital representation of the controlled processes. The radiofrequency (RF) ion source installed at the axial injection line of the cyclotron produced ion beams of HD{sup +}, HT{sup +}, DT{sup +}, D{sub 2}H{sup +}, etc. At a several months DT{sup +} beam acceleration the tritium consumption was less than 108 Bq/hr. The intensity of a 58.2 MeV triton beam (T{sup +} ions) extracted from the cyclotron chamber was about 10 nA.

  11. Recent advances in SRS on hydrogen isotope separation using thermal cycling absorption process

    SciTech Connect

    Xiao, X.; Kit Heung, L.; Sessions, H.T.

    2015-03-15

    TCAP (Thermal Cycling Absorption Process) is a gas chromatograph in principle using palladium in the column packing, but it is unique in the fact that the carrier gas, hydrogen, is being isotopically separated and the system is operated in a semi-continuous manner. TCAP units are used to purify tritium. The recent TCAP advances at Savannah River Site (SRS) include compressor-free concept for heating/cooling, push and pull separation using an active inverse column, and compact column design. The new developments allow significantly higher throughput and better reliability from 1/10 of the current production system's footprint while consuming 60% less energy. Various versions are derived in the meantime for external customers to be used in fusion energy projects.

  12. DEMONSTRATION OF THE NEXT-GENERATION TCAP HYDROGEN ISOTOPE SEPARATION PROCESS

    SciTech Connect

    Heung, L; Henry Sessions, H; Steve Xiao, S; Heather Mentzer, H

    2009-01-09

    The first generation of TCAP hydrogen isotope separation process has been in service for tritium separation at the Savannah River Site since 1994. To prepare for replacement, a next-generation TCAP process has been developed. This new process simplifies the column design and reduces the equipment requirements of the thermal cycling system. An experimental twelve-meter column was fabricated and installed in the laboratory to demonstrate its performance. This new design and its initial test results were presented at the 8th International Conference on Tritium Science and Technology and published in the proceedings. We have since completed the startup and demonstration the separation of protium and deuterium in the experimental unit. The unit has been operated for more than 200 cycles. A feed of 25% deuterium in protium was separated into two streams each better than 99.7% purity.

  13. Measurements of galactic hydrogen and helium isotopes from 1978 through 1983

    NASA Technical Reports Server (NTRS)

    Evenson, P.; Kroeger, R.; Meyer, P.; Miller, D.

    1985-01-01

    The differential flux of the hydrogen and helium isotopes was measured using an instrument on the ISEE-3 spacecraft during solar quiet time periods from August 1978 through December 1983. These measurements cover the energy range from 26 MeV/nucleon through 138 MeV/nucleon for both H-1 and He-4, from 24 to 89 MeV/nucleon for H-2, and from 43 to 146 solar activity varied from near minimum to maximum conditions causing the observed flux of galactic cosmic rays to modulate by an order of magnitude. To describe the propagation in the galaxy, it was found that the standard leaky box approximation with an escape path length of 6.7 g/sq cms forms a self consistent model for the light cosmic ray nuclei at the observed energies.

  14. Hydrogen isotope ratios of palmitic acid in lacustrine sediments record late Quaternary climate variations

    NASA Astrophysics Data System (ADS)

    Huang, Yongsong; Shuman, Bryan; Wang, Yi; Webb, Thompson, III

    2002-12-01

    The rich paleoclimate information preserved in lacustrine sedimentary organic matter can be difficult to extract because of the mixed terrestrial and aquatic inputs. Herein we demonstrate that compound-specific hydrogen isotope analysis of palmitic acid, (PA), a ubiquitous compound in lacustrine sediments, captures the δD signals of lake water. Samples collected across a diverse range of 33 North American lakes show a strong correlation between water and δDPA values. At Crooked Pond, Massachusetts, the δDPA changes in a 14 k.y. sediment record parallel temperature trends inferred from fossil pollen. Downcore changes reveal differences between climatic trends in New England and in Greenland that are consistent with important regional differences in climate controls.

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

    NASA Astrophysics Data System (ADS)

    Wolhowe, M. D.; Prahl, F. G.; Probert, I.; Maldonado, M.

    2009-04-01

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

  16. Stabilization of CH2 on Ru(0001) by hydrogen co-adsorption

    NASA Astrophysics Data System (ADS)

    Levchenko, Sergey V.; Zhao, Xunhua; Scheffler, Matthias; Fritz-Haber-Institut der MPG, Berlin Team

    2015-03-01

    Based on indirect experimental evidence, CH2 was proposed as a buidling block for hydrocarbon chain growth on the Ru(0001) surface during the Fischer-Tropsch process. However, previous calculations agreed that CH2 is not stable on Ru(0001) at the reaction conditions, and should quickly convert into CH. Employing density-functional theory, we show that this disagreement can be reconciled if coadsorbed hydrogen is present on the surface. The atomic structure of various CHx+Hy phases is obtained with genetic algorithm. CHx dissociation barriers are calculated using the string method. We further demonstrate, by calculating the surface phase diagram for one-carbon species on Ru(0001) as a function of H2 chemical potential, that the stabilization of CH2 by co-adsorbed hydrogen requires non-equilibrium conditions. The calculated barrier for the CH2 dissociation in the presence of hydrogen is significantly increased, and is close to the one recently measured by vibrational sum-frequency generation spectroscopy. Our results also explain why CH2 was not observed when C or CH are hydrogenated on Ru(0001), although it is observed after methane decomposition.

  17. High temperature hydrogen sulfide adsorption on activated carbon - I. Effects of gas composition and metal addition

    USGS Publications Warehouse

    Cal, M.P.; Strickler, B.W.; Lizzio, A.A.

    2000-01-01

    Various types of activated carbon sorbents were evaluated for their ability to remove H2S from a simulated coal gas stream at a temperature of 550 ??C. The ability of activated carbon to remove H2S at elevated temperature was examined as a function of carbon surface chemistry (oxidation, thermal desorption, and metal addition), and gas composition. A sorbent prepared by steam activation, HNO3 oxidation and impregnated with Zn, and tested in a gas stream containing 0.5% H2S, 50% CO2 and 49.5% N2, had the greatest H2S adsorption capacity. Addition of H2, CO, and H2O to the inlet gas stream reduced H2S breakthrough time and H2S adsorption capacity. A Zn impregnated activated carbon, when tested using a simulated coal gas containing 0.5% H2S, 49.5% N2, 13% H2, 8.5% H2O, 21% CO, and 7.5% CO2, had a breakthrough time of 75 min, which was less than 25 percent of the length of breakthrough for screening experiments performed with a simplified gas mixture of 0.5% H2S, 50% CO2, and 49.5% N2.

  18. Divacancy-assisted transition metal adsorption on the BN graphene and its interaction with hydrogen molecules: a theoretical study

    NASA Astrophysics Data System (ADS)

    Chen, Ying; Wang, Hongmei; Wang, Hongxia; Zhao, Jing-xiang; Cai, Qing-hai; Wang, Xiao-Guang; Ding, Yi-hong

    2013-05-01

    We have performed first-principles calculations to study the chemical functionalization of the BN graphene with divacancy (DV) defect by 12 different transition metal (TM) atoms, including Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pt, and Au. The results indicate that the DV defect can assist the adsorption of TM atoms on BN graphene. Moreover, some impurity bands are induced within the band gap of DV-BN graphene, leading to the modification of its electronic properties in various ways. Interestingly, Ti- and Co-adsorbed DV-BN graphenes are found to possess ferromagnetic characteristic, while antiferromagnetic state is preferred for V-, Mn-, and Fe-functionalized DV-BN graphenes, and the paramagnetic state is the ground state for Sc-, Cr-, Ni-, Cu, Zn-, Pt-, and Au-decorated DV-BN graphenes. Finally, aiming at evaluating the potential of these functionalized BN graphenes in hydrogen storage, we study their interaction with H2 molecules. It is found that the dispersed Sc, V, and Cr on DV-BN graphene are able to adsorb up to three H2 molecules as strongly as 0.25-0.58 eV/H2, suggesting that the three nanomaterials may be suitable candidates for hydrogen storage.

  19. Leaf waxes in riparian trees: hydrogen isotopes, concentrations, and chain-length patterns

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Ehleringer, J.; Doman, C.; Khachaturyan, S.

    2011-12-01

    The stable hydrogen isotope ratios of epicuticular leaf wax n-alkanes record aspects of a plant's ecophysiological conditions. However, it remains unclear as to whether n-alkane hydrogen isotope values (δ2H) directly reflect environmental water (source water or tissue water) or environmental water in combination with a biochemical fractionation. Furthermore, it is uncertain if leaf n-alkane δ2H values reflect a single time interval during leaf expansion or if n-alkane δ2H values record the combination of inputs throughout the entire lifespan of a leaf. These different possibilities will influence how leaf wax biomarkers are interpreted in both ecological and environmental reconstruction contexts. To address these issues, we sampled leaves/buds, stems, and water sources of five common western U.S. riparian species under natural field conditions throughout the growing season. Riparian species were selected because the input water source is most likely to be nearly constant through the growing season. We found that species in this study demonstrated marked and systematic variations in n-alkane concentration, average chain length, and δ2H values. Intraspecific patterns were consistent: average chain lengths and δ2H values increased from bud opening through full leaf expansion with little variation during the remainder of the sampling interval, while leaf-wax concentration as a fraction of total biomass increased throughout the growing season. These data imply that leaf-wax δ2H values reflect multiple periods of wax growth and that the leaf wax is continually produced throughout a leaf's lifespan.

  20. Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

    SciTech Connect

    Zou, Chenyu; van Duin, Adri C.T.; Sorescu, Dan C.

    2012-06-01

    We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer–Tropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H{sub 2} and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.

  1. An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, T.B.

    2001-01-01

    An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2H/1H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H3+ contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: -630??? to -790??? for the second gas and -368??? to -462??? for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the ?? values so that the gases with the lowest and highest 2H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85???. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate. ?? Springer-Verlag 2001.

  2. Orbital-scale summer precipitation and temperature variability in central China reconstructed with leaf wax hydrogen isotopes and branched GDGTs

    NASA Astrophysics Data System (ADS)

    Thomas, E. K.; Clemens, S. C.; Prell, W. L.; Sun, Y.; Huang, Y.

    2013-12-01

    Reconstructions of monsoon variability on orbital time scales inform how the monsoon responds to large variations in forcing mechanisms (e.g., insolation, ice volume, greenhouse gases). The timing, or phase, of proxy response relative to forcing mechanisms (e.g., maximum insolation, maximum ice volume) can provide insights into which mechanisms control monsoon variability. Furthermore, obtaining summer monsoon records from different regions of Asia provides information about the spatial expression of monsoon variability. Deciphering which mechanisms control orbital-scale summer monsoon variability, however, requires reconstructions using proxies that respond mainly to summer monsoon variability. We present a 300-kyr-long, millennial-resolution record of Pleistocene summer monsoon precipitation variability on the Chinese Loess Plateau, generated using leaf wax hydrogen isotopes. The loess plateau receives ca. 50% of total annual precipitation during the summer monsoon, and plants produce leaf waxes during the warm, wet summer months. Thus, leaf wax hydrogen isotopes reflect summer precipitation isotopes. Precipitation isotopes change in response to changes in transport history (e.g. source water isotope ratios, transport path, etc.), which is influenced by changes in monsoon strength. Precipitation isotopes are also affected by local condensation temperature, which we account for using an independent temperature proxy, branched glycerol dialkyl glycerol tetraethers. We present these independent monsoon and temperature records and examine implications for mechanisms controlling monsoon variability in central China.

  3. Search for isobar-analog states of superheavy hydrogen isotopes5-7He

    NASA Astrophysics Data System (ADS)

    Chernyshev, B. A.; Gurov, Yu B.; Korotkova, L. Yu; Kuznetsov, D. S.; Lapushkin, S. V.; Tel'kushev, M. V.; Schurenkova, T. D.

    2016-02-01

    Search for isobar-analog states (IAS) of superheavy hydrogen isotopes 5-7H was performed among the high-excited states of helium isotopes 5-7He. The excited spectra were measured in stopped pion absorption by light nuclei. The experiment was performed at low energy pion channel of LANL with two-arm multilayer semiconductor spectrometer. Excited states of 5-7He were observed in three-body reaction channels on 10,11B nuclei. Several excited levels were observed for the first time. 6He excited state with Ex = 27.0(8) MeV observed in 10B(π-,pt)X channel is an IAS candidate for 6H with Er ∼ 5.5 MeV. 7He excited state with Ex = 24.8(4) MeV observed in 10B(π-,pd)X, nB(π-,pt)X and nB(π-,dd)X channels is an IAS candidate for 7H with Er ∼ 3 MeV.

  4. Mean annual temperatures of mid-latitude regions derived from stable hydrogen isotopes of wood lignin

    NASA Astrophysics Data System (ADS)

    Anhäuser, Tobias; Greule, Markus; Bowen, Gabriel J.; Keppler, Frank

    2016-04-01

    Tree rings are widely used climate archives providing annual resolutions on centennial to millennial timescales. Besides plant physiological parameters such as tree-ring width or maximum latewood density, stable isotope compositions (expressed as δ values) complement or even broaden the potential of the climate archive tree rings. A considerable wood constituent are ether-bonded methoxyl groups as part of lignin which can be used for stable hydrogen isotope studies. The δ²H value of the lignin methoxyl groups reflects the δ²H value of the tree source water as a result of a large uniform fractionation. Hence, this relation can be used to infer δ²H values of precipitation which are in temperate regions primarily controlled by temperature. Here, we measured δ²H values of lignin methoxyl groups (n = 111) of tree rings from various species collected along a ~3500 km north-south transect across Europe with mean annual temperatures (MAT) ranging from ‑4 to +17 °C. We found a significant linear correlation between δ²H values of the lignin methoxyl groups and MAT (R² = 0.81, p < 0.01). We used this relationship to predict MATs from randomly collected wood samples and found general agreement between predicted and observed MATs for the mid-latitudes on a global scale. Thus our results indicate that δ²H values of lignin methoxyl groups are a promising tool for mid-latitude temperature reconstruction of the Holocene.

  5. Hydrogen Isotopes as a Sentinel of Biological Invasion by the Japanese Beetle, Popillia japonica (Newman)

    PubMed Central

    Ogle, Kiona; Caron, Melanie; Marks, Jane C.; Rogg, Helmuth W.

    2016-01-01

    Invasive species alter ecosystems, threaten native and endangered species, and have negative economic impacts. Knowing where invading individuals are from and when they arrive to a new site can guide management. Here, we evaluated how well the stable hydrogen isotope composition (δ2H) records the recent origin and time since arrival of specimens of the invasive Japanese beetle (Popillia japonica Newman) captured near the Portland International Airport (Oregon, U.S.A.). The δ2H of Japanese beetle specimens collected from sites across the contiguous U.S.A. reflected the δ2H of local precipitation, a relationship similar to that documented for other organisms, and one confirming the utility of δ2H as a geographic fingerprint. Within weeks after experimental relocation to a new isotopic environment, the δ2H of beetles changed linearly with time, demonstrating the potential for δ2H to also mark the timing of arrival to a new location. We used a hierarchical Bayesian model to estimate the recent geographical origin and timing of arrival of each specimen based on its δ2H value. The geographic resolution was broad, with values consistent with multiple regions of origin in the eastern U.S.A., slightly favoring the southeastern U.S.A. as the more likely source. Beetles trapped from 2007–2010 had arrived 30 or more days prior to trapping, whereas the median time since arrival declined to 3–7 days for beetles trapped from 2012–2014. This reduction in the time between arrival and trapping at the Portland International Airport supports the efficacy of trapping and spraying to prevent establishment. More generally, our analysis shows how stable isotopes can serve as sentinels of biological invasions, verifying the efficacy of control measures, or, alternatively, indicating when those measures show signs of failure. PMID:26959686

  6. Hydrogen Isotopes as a Sentinel of Biological Invasion by the Japanese Beetle, Popillia japonica (Newman).

    PubMed

    Hungate, Bruce A; Kearns, Diana N; Ogle, Kiona; Caron, Melanie; Marks, Jane C; Rogg, Helmuth W

    2016-01-01

    Invasive species alter ecosystems, threaten native and endangered species, and have negative economic impacts. Knowing where invading individuals are from and when they arrive to a new site can guide management. Here, we evaluated how well the stable hydrogen isotope composition (δ2H) records the recent origin and time since arrival of specimens of the invasive Japanese beetle (Popillia japonica Newman) captured near the Portland International Airport (Oregon, U.S.A.). The δ2H of Japanese beetle specimens collected from sites across the contiguous U.S.A. reflected the δ2H of local precipitation, a relationship similar to that documented for other organisms, and one confirming the utility of δ2H as a geographic fingerprint. Within weeks after experimental relocation to a new isotopic environment, the δ2H of beetles changed linearly with time, demonstrating the potential for δ2H to also mark the timing of arrival to a new location. We used a hierarchical Bayesian model to estimate the recent geographical origin and timing of arrival of each specimen based on its δ2H value. The geographic resolution was broad, with values consistent with multiple regions of origin in the eastern U.S.A., slightly favoring the southeastern U.S.A. as the more likely source. Beetles trapped from 2007-2010 had arrived 30 or more days prior to trapping, whereas the median time since arrival declined to 3-7 days for beetles trapped from 2012-2014. This reduction in the time between arrival and trapping at the Portland International Airport supports the efficacy of trapping and spraying to prevent establishment. More generally, our analysis shows how stable isotopes can serve as sentinels of biological invasions, verifying the efficacy of control measures, or, alternatively, indicating when those measures show signs of failure. PMID:26959686

  7. Oxygen and hydrogen isotope variations in the Pecos River of American Southwest

    NASA Astrophysics Data System (ADS)

    Yuan, F.; Miyamoto, S.

    2006-12-01

    The Pecos River is located in eastern New Mexico and western Texas, and its salinity increases downstream. Oxygen and hydrogen isotopic compositions (δ18O and δD) were measured on surface waters sampled from the Pecos River and its tributaries in March, May, and July of 2005. The measurements show considerably large variations in δ18O and δD, ranging from a δ18O of - 8.9‰ and δD of -64.5‰ in March at Salt Creek to a δ18O of 3.6‰ and δD of 1.6‰ in July at Girvin. Many surface waters except for head and tail waters have negative values of deuterium excess (dexcess=δD-8δ18O). Combined with the existing stable isotopic data from three gaging stations along the Pecos River (Santa Rosa, Red Bluff and Langtry) collected by the U.S. Geological Survey, it appears that evaporative enrichments of heavier isotopic species (O-18 and D) are more evident in the middle section than other parts of the river. δ18O and δD decrease at Langtry due to substantial increases in local runoff. The enhanced evaporation in the middle Pecos River is probably ascribed to a prolonged residence time resulting from anthropogenic perturbations (e.g., multi-cycle irrigation water uses and water impoundments in typically shallow reservoirs). Additionally, natural topographical gradients may have played a role in affecting water residence time and the amount of water evaporated from watersheds. These observations suggest that high dissolved salt contents of the Pecos River can be attributed to intense evaporation besides dissolution of geological salt deposits.

  8. The influence of environmental water on the hydrogen stable isotope ratio in aquatic consumers.

    PubMed

    Solomon, Christopher T; Cole, Jonathan J; Doucett, Richard R; Pace, Michael L; Preston, Nicholas D; Smith, Laura E; Weidel, Brian C

    2009-08-01

    Aquatic food webs are subsidized by allochthonous resources but the utilization of these resources by consumers can be difficult to quantify. Stable isotope ratios of hydrogen (deuterium:hydrogen; deltaD) potentially distinguish allochthonous inputs because deltaD differs between terrestrial and aquatic primary producers. However, application of this tracer is limited by uncertainties regarding the trophic fractionation of deltaD and the contributions of H from environmental water (often called "dietary water") to consumer tissue H. We addressed these uncertainties using laboratory experiments, field observations, modeling, and a literature synthesis. Laboratory experiments that manipulated the deltaD of water and food for insects, cladoceran zooplankton, and fishes provided strong evidence that trophic fractionation of deltaD was negligible. The proportion of tissue H derived from environmental water was substantial yet variable among studies; estimates of this proportion, inclusive of lab, field, and literature data, ranged from 0 to 0.39 (mean 0.17 +/- 0.12 SD). There is a clear need for additional studies of environmental water. Accounting for environmental water in mixing models changes estimates of resource use, although simulations suggest that uncertainty about the environmental water contribution does not substantially increase the uncertainty in estimates of resource use. As long as this uncertainty is accounted for, deltaD may be a powerful tool for estimating resource use in food webs. PMID:19471971

  9. Cultivation-independent detection of autotrophic hydrogen-oxidizing bacteria by DNA stable-isotope probing.

    PubMed

    Pumphrey, Graham M; Ranchou-Peyruse, Anthony; Spain, Jim C

    2011-07-01

    Knallgas bacteria are a physiologically defined group that is primarily studied using cultivation-dependent techniques. Given that current cultivation techniques fail to grow most bacteria, cultivation-independent techniques that selectively detect and identify knallgas bacteria will improve our ability to study their diversity and distribution. We used stable-isotope probing (SIP) to identify knallgas bacteria in rhizosphere soil of legumes and in a microbial mat from Obsidian Pool in Yellowstone National Park. When samples were incubated in the dark, incorporation of (13)CO(2) was H(2) dependent. SIP enabled the detection of knallgas bacteria that were not detected by cultivation, and the majority of bacteria identified in the rhizosphere soils were betaproteobacteria predominantly related to genera previously known to oxidize hydrogen. Bacteria in soil grew on hydrogen at concentrations as low as 100 ppm. A hydB homolog encoding a putative high-affinity NiFe hydrogenase was amplified from (13)C-labeled DNA from both vetch and clover rhizosphere soil. The results indicate that knallgas bacteria can be detected by SIP and populations that respond to different H(2) concentrations can be distinguished. The methods described here should be applicable to a variety of ecosystems and will enable the discovery of additional knallgas bacteria that are resistant to cultivation. PMID:21622787

  10. An innovative molybdenum column liner for oxygen and hydrogen stable isotope analysis by pyrolysis.

    PubMed

    Stuart-Williams, Hilary; Wong, S Chin; Farquhar, Graham D; Keitel, Claudia; Clayton, Stephen

    2008-04-01

    The most widely used method for pyrolysing samples for hydrogen or oxygen isotopic analysis involves heating them to greater than 1300 degrees C in a helium stream passed through a glassy carbon tube in an alumina casing. There are a number of difficulties with this. Glassy carbon tubes are expensive and interaction between the carbon tube and the outer casing produces unwanted carbon monoxide by reduction of the alumina at high temperatures. The latter effect is overwhelming if temperatures of 1400 degrees C or greater are used for pyrolysis. We experimented with lining alumina casings with pure molybdenum sheet. It is relatively cheap, conforms well to the interior of the reactor tube (to avoid carrier and sample bypassing of the carbon pack), resists high temperatures and neither oxidises excessively nor absorbs the gases. The main disadvantages are that silver sample cups must be used and that the molybdenum degrades over time by formation of the carbide. We can maintain sharp peaks, high precision and good accuracy over more than 700 solid samples for both hydrogen and oxygen. The reactors last longer for water injections. The molybdenum in the columns does not contribute greatly to memory effects. The precision of analysis is dependent on other factors as well as the pyrolysis column, but for oxygen we typically achieve approximately <0.2 per thousand (sucrose), <0.25 per thousand (water) and <0.25 per thousand (leaf), sometimes using only a linear correction of drift, after dividing the run into 1 to 3 segments. PMID:18335516

  11. Examining the Utility of Stable Hydrogen Isotopes in Aquatic Food-Web Ecology

    NASA Astrophysics Data System (ADS)

    Doucett, R. R.; Blinn, D. W.; Caron, M.; Ellis, B. K.; Marks, J. C.; Hungate, B. A.

    2005-05-01

    The utility of stable hydrogen isotopes (dD) in hydrology and terrestrial ecology is well understood, but it has not been sufficiently examined in the field of aquatic ecology. Here, we present initial results from: (1) the Colorado River (AZ), Fossil Creek (AZ) and Devil's Hole (NV), where we examined the usefulness of dD to distinguish between allochthonous and autochthonous inputs to aquatic food webs, and (2) from the Sopochnaya River, Russia, where we tested the ability of dD to discern between anadromous and freshwater steelhead trout. In general, aquatic inputs (-320 to -168 per mil) were much more depleted than terrestrial inputs (-166 to -105 per mil). Macroinvertebrates displayed dD values similar to presumed food sources (e.g., baetid mayflies ranged from -299 to -222 per mil). In some cases, mixing models suggested that dD was a better predictor of food-source origin than d13C. As expected, dD values for anadromous trout (-121 to -103 per mil) were more enriched than those of freshwater residents (-161 to -123 per mil), and strong correlations existed between dD, d34S, and d13C. Methodological considerations (e.g., exchangeable hydrogen) and certain assumptions (e.g., importance of food vs. water on tissue dD) will be discussed.

  12. Is modern climate variability reflected in compund specific hydrogen isotope ratios of sedimentary biomarkers?

    NASA Astrophysics Data System (ADS)

    Sachse, D.; Radke, J.; Gleixner, G.

    2003-04-01

    Compound specific hydrogen isotope ratios are emerging as a new palaeoclimatic and palaeohydrological proxy. First reconstructions of palaeoclimate using D/H ratios from n-alkanes are available (Andersen et al. 2001, Sauer et al. 2001, Sachse et al. 2003). However, a systematic approach comparing recent sedimentary biomarkers with climate data is still lacking. We are establishing an ecosystem study of small, ground water fed lakes with known limnology. Nearly all lakes are close to a long-term climate-monitoring site (CARBOEUROPE flux tower site, IAEA precipitation monitoring) delivering ecophysiological and climatic data as temperature, precipitation, evapotranspiration etc. Water, primary biomass, plant, soil and sediment were sampled from lakes and the surrounding ecosystem along a climatic and isotopic gradient in meteoric waters from northern Finland (deltaD: -130 permil vs. VSMOW) to southern Italy (deltaD: -30 permil vs. VSMOW, IAEA 2001). Biomarkers were extracted from the samples to test if climatic variability is reflected in their D/H ratios. First results of the factors influencing the hydrogen isotope composition of sedimentary biomarkers and their use as palaeoclimatic and palaeohydrological proxy will be presented. Andersen N, Paul HA, Bernasconi SM, McKenzie JA, Behrens A, Schaeffer P, Albrecht P (2001) Large and rapid climate variability during the Messinian salinity crisis: Evidence from deuterium concentrations of individual biomarkers. Geology 29:799-802 IAEA (2001) GNIP Maps and Animations. International Atomic Energy Agency, Vienna. Accessible at http://isohis.iaea.org Sachse D, Radke J, Gaupp R, Schwark L, Lüniger G, Gleixner G (2003) Reconstruction of palaeohydrological conditions in a lagoon during the 2nd Zechstein cycle through simultaneous use of deltaD values of individual n-alkanes and delta18O and delta13C values of carbonates. International Journal of Earth Sciences, submitted Sauer PE, Eglington TI, Hayes JM, Schimmelman A

  13. Cathodic adsorptive stripping voltammetric determination of uranium with potassium hydrogen phthalate.

    PubMed

    Farghaly, O A; Ghandour, M A

    1999-06-01

    The adsorption properties of dioxouranium (II)-Phathalate complexes onto hanging mercury drop electrode are exploited in developing a highly sensitive and selective stripping voltammetric procedure for the determination of uranium (VI). The reduction current of adsorbed complex ions of U(VI) was measured by both linear sweep (LSCSV) and differential pulse cathodic stripping voltammetry (DPCSV), preceded by a period of preconcentration onto the electrode surface. As low as 2x10(-9) mol dm(-3) (0.5 mug/l) and 2x10(-8) mol dm(-3) (4.8 mug/l) with accumulation time 240 and 120 s using DPCSV and LSCSV, respectively, have been determined successfully. The relative standard deviation of 2.2% at the 5 ppm level was obtained. The interferences of some metal ions and anions were studied. The application of this method was tested in the determination of uranium in superphosphate fertilizer. PMID:18967571

  14. Electronic structure of graphene on a reconstructed Pt(100) surface: Hydrogen adsorption, doping, and band gaps

    NASA Astrophysics Data System (ADS)

    Ulstrup, Søren; Nilsson, Louis; Miwa, Jill A.; Balog, Richard; Bianchi, Marco; Hornekær, Liv; Hofmann, Philip

    2013-09-01

    We probe the structure and electronic band structure of graphene grown on a Pt(100) substrate using scanning tunneling microscopy, low energy electron diffraction, and angle-resolved photoemission spectroscopy. It is found that the graphene layer lacks a well-defined azimuthal orientation with respect to the substrate, causing a circular smearing of the π band instead of a well-defined Dirac cone near the Fermi level. The graphene is found to be electron doped placing the Dirac point ˜0.45 eV below the Fermi level, and a gap of 0.15±0.03 eV is found at the Dirac point. We dose atomic hydrogen and monitor the coverage on the graphene by analyzing the impurity-induced broadening of the π-band width. Saturation of graphene on Pt(100) with hydrogen does not expand the band gap, but instead hydrogen-mediated broadening and rehybridization of the graphene sp2 bonds into sp3 leads to a complete disruption of the graphene π band, induces a lifting of the Pt(100) reconstruction, and introduces a dispersing Pt state near the Fermi level. Deposition of rubidium on graphene on Pt(100) leads to further electron doping, pushing the Dirac point to a binding energy of ˜1.35 eV, and increasing the band gap to 0.65±0.04 eV.

  15. Effect of surface characteristics of wood-based activated carbons on adsorption of hydrogen sulfide

    SciTech Connect

    Adib, F.; Bagreev, A.; Bandosz, T.J.

    1999-06-15

    Three wood-based commercial activated carbons supplied by Westvaco were studied as adsorbents of hydrogen sulfide. The initial materials were characterized using sorption of nitrogen, Boehm titration, potentiometric titration, water sorption, thermal analysis, and temperature-programmed desorption. The breakthrough tests were done at low concentrations of H{sub 2}S in the input gas to simulate conditions in water pollution control plants where carbon beds are used as odor adsorbents. In spite of apparent general similarities in the origin of the materials, method of activation, surface chemistry, and porosity, significant differences in their performance as hydrogen sulfide adsorbents were observed. Results show that the combined effect of the presence of pores large enough to accommodate surface functional groups and small enough to have the film of water at relatively low pressure contributes to oxidation of hydrogen sulfide. Moreover, there are features of activated carbon surfaces such as local environment of acidic/basic groups along with the presence of alkali metals which are important to the oxidation process.

  16. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2012-10-01

    Biologically produced molecular hydrogen (H2) is characterised by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of H2. Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δ D from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. In a first set of experiments, we investigated δ D of H2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δ D = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δ DH2O= +73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰) between H2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of δ D = -728‰ (±28‰), and a fractionation constant ϵH2-H2O of -711‰ (±34‰) between H2 and the water. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for δ D of H2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and

  17. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds. PMID:18728883

  18. Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

    2013-01-01

    The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes

  19. [Hydrogen and oxygen isotopes of lake water and geothermal spring water in arid area of south Tibet].

    PubMed

    Xiao, Ke; Shen, Li-Cheng; Wang, Peng

    2014-08-01

    The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes. PMID:25338365

  20. Diffusion, adsorption, and desorption of molecular hydrogen on graphene and in graphite.

    PubMed

    Petucci, Justin; LeBlond, Carl; Karimi, Majid; Vidali, Gianfranco

    2013-07-28

    The diffusion of molecular hydrogen (H2) on a layer of graphene and in the interlayer space between the layers of graphite is studied using molecular dynamics computer simulations. The interatomic interactions were modeled by an Adaptive Intermolecular Reactive Empirical Bond Order (AIREBO) potential. Molecular statics calculations of H2 on graphene indicate binding energies ranging from 41 meV to 54 meV and migration barriers ranging from 3 meV to 12 meV. The potential energy surface of an H2 molecule on graphene, with the full relaxations of molecular hydrogen and carbon atoms is calculated. Barriers for the formation of H2 through the Langmuir-Hinshelwood mechanism are calculated. Molecular dynamics calculations of mean square displacements and average surface lifetimes of H2 on graphene at various temperatures indicate a diffusion barrier of 9.8 meV and a desorption barrier of 28.7 meV. Similar calculations for the diffusion of H2 in the interlayer space between the graphite sheets indicate high and low temperature regimes for the diffusion with barriers of 51.2 meV and 11.5 meV. Our results are compared with those of first principles. PMID:23902002