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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsuyama, M.; Kondo, M.; Noda, N.

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 ismore » 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)« less

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.

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.

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.

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.

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

Adsorption of hydrogen gas and redox processes in clays.

PubMed

Didier, Mathilde; Leone, Laura; Greneche, Jean-Marc; Giffaut, Eric; Charlet, Laurent

2012-03-20

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.

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)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina

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-principlesmore » 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.« less

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.

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

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.

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.

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.

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.

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.

Transport hysteresis and hydrogen isotope effect on confinement

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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.

Hydrogen isotope fractionation during lipid biosynthesis by Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, Sitindra S.; Pagani, Mark

2013-10-01

We studied the controls on the fractionation of hydrogen isotopes during lipid biosynthesis by Haloarcula marismortui, a halophilic archaea, in pure culture experiments by varying organic substrate, the hydrogen isotope composition (D/H) of water, temperature, and salinity. Cultures were grown on three substrates: succinate, pyruvate and glycerol with known hydrogen isotope compositions, and in water with different hydrogen isotopic compositions. All culture series grown on a particular substrate show strong correlations between δDarchaeol and δDwater. However, correlations are distinctly different for cultures grown on different substrates. Our results indicate that the metabolic pathway of substrate exerts a fundamental influence on the δD value of lipids, likely by influencing the D/H composition of NADPH (nicotinamide adenine dinucleotide phosphate), the reducing agent that contributes hydrogen to carbon atoms during lipid biosynthesis. Temperature and salinity have smaller, but similar effects on δDlipid, primarily due to the way temperature and salinity influence growth rate, as well as temperature effects on the activity of enzymes.

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.

Isotopic exchange of hydrogen in aromatic amino acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 exchangemore » of hydrogen is discussed. 17 refs., 2 figs., 2 tabs.« less

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

NASA Astrophysics Data System (ADS)

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

2010-03-01

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

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.

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

Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

NASA Astrophysics Data System (ADS)

Larson, T. E.

2012-12-01

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

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

USDA-ARS?s Scientific Manuscript database

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

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.

Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons.

PubMed

Kim, Byung-Joo; Park, Soo-Jin

2007-07-15

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.

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.

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

PubMed

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

2017-10-25

Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ∼26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D 2 through direct selective separation studies using 1:1 D 2 /H 2 mixtures.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Carbon and hydrogen isotope fractionation by moderately thermophilic methanogens

NASA Astrophysics Data System (ADS)

Valentine, David L.; Chidthaisong, Amnat; Rice, Andrew; Reeburgh, William S.; Tyler, Stanley C.

2004-04-01

A series of laboratory studies were conducted to increase understanding of stable carbon (13C/12C) and hydrogen (D/H) isotope fractionation arising from methanogenesis by moderately thermophilic acetate- and hydrogen-consuming methanogens. Studies of the aceticlastic reaction were conducted with two closely related strains of Methanosaeta thermophila. Results demonstrate a carbon isotope fractionation of only 7‰ (α = 1.007) between the methyl position of acetate and the resulting methane. Methane formed by this process is enriched in 13C when compared with other natural sources of methane; the magnitude of this isotope effect raises the possibility that methane produced at elevated temperature by the aceticlastic reaction could be mistaken for thermogenic methane based on carbon isotopic content. Studies of H2/CO2 methanogenesis were conducted with Methanothermobacter marburgensis. The fractionation of carbon isotopes between CO2 and CH4 was found to range from 22 to 58‰ (1.023 ≤ α ≤ 1.064). Greater fractionation was associated with low levels of molecular hydrogen and steady-state metabolism. The fractionation of hydrogen isotopes between source H2O and CH4 was found to range from 127 to 275‰ (1.16 ≤ α ≤ 1.43). Fractionation was dependent on growth phase with greater fractionation associated with later growth stages. The maximum observed fractionation factor was 1.43, independent of the δD-H2 supplied to the culture. Fractionation was positively correlated with temperature and/or metabolic rate. Results demonstrate significant variability in both hydrogen and carbon isotope fractionation during methanogenesis from H2/CO2. The relatively small fractionation associated with deuterium during H2/CO2 methanogenesis provides an explanation for the relatively enriched deuterium content of biogenic natural gas originating from a variety of thermal environments. Results from these experiments are used to develop a hypothesis that differential

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

PubMed

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

2017-08-01

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

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.

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.

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

NASA Astrophysics Data System (ADS)

Dirghangi, S. S.; Pagani, M.

2010-12-01

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

Adsorption isotope effects of water on mesoporous silica and alumina with implications for the land-vegetation-atmosphere system

NASA Astrophysics Data System (ADS)

Lin, Ying; Horita, Juske; Abe, Osamu

2018-02-01

Soil water dynamics within a vadose (unsaturated) zone is a key component in the hydrologic cycle, especially in arid regions. In applying the Craig-Gordon evaporation model to obtain isotopic compositions of soil water and the evaporated vapor in land-surface models (LSMs), it has been assumed that the equilibrium isotope fractionation factors between soil water and water vapor, α(2H) and α(18O), are identical to those between liquid and vapor of bulk water. Isotope effects in water condensation arise from intermolecular hydrogen bonding in the condensed phase and the appearance of hindered rotation/translation. Hydrogen bonding between water molecules and pore surface hydroxyl groups influences adsorption isotope effects. To test whether equilibrium fractionation factors between soil water and water vapor are identical to those between liquid and vapor of bulk water and to evaluate the influence of pore size and chemical composition upon adsorption isotope effects, we extended our previous experiments of a mesoporous silica (15 nm) to two other mesoporous materials, a silica (6 nm) and an alumina (5.8 nm). Our results demonstrated that α(2H) and α(18O) between adsorbed water and water vapor are 1.057 and 1.0086 for silica (6 nm) and 1.041 and 1.0063 for alumina (5.8 nm), respectively, at saturation pressure (po), which are smaller than 1.075 and 1.0089, respectively, between liquid and vapor phases of free water at 30 °C and that the differences exaggerate at low water contents. However, the profiles of α values with relative pressures (p/po) for these three materials differ due to the differences in chemical compositions and pore sizes. Empirical formula relating α(2H) and α(18O) values to the proportions of filled pores (f) are developed for potential applications to natural soils. Our results from triple oxygen isotope analyses demonstrated that the isotope fractionation does not follow a canonical law. For the silica (15 nm), fractionation exponents

Compact determination of hydrogen isotopes

DOE PAGES

Robinson, David

2017-04-06

Scanning calorimetry of a confined, reversible hydrogen sorbent material has been previously proposed as a method to determine compositions of unknown mixtures of diatomic hydrogen isotopologues and helium. Application of this concept could result in greater process knowledge during the handling of these gases. Previously published studies have focused on mixtures that do not include tritium. This paper focuses on modeling to predict the effect of tritium in mixtures of the isotopologues on a calorimetry scan. Furthermore, the model predicts that tritium can be measured with a sensitivity comparable to that observed for hydrogen-deuterium mixtures, and that under so memore » conditions, it may be possible to determine the atomic fractions of all three isotopes in a gas mixture.« less

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Noncovalent Hydrogen Isotope Effects

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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.

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

DOE PAGES

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

2016-08-03

The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag 0Z) 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 Ag 0Z 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 iodinemore » adsorption was through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag 0Z 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

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.

Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

NASA Astrophysics Data System (ADS)

Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

2018-05-01

In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

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

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Spin switch in iron phthalocyanine on Au(111) surface by hydrogen adsorption

NASA Astrophysics Data System (ADS)

Wang, Yu; Li, Xiaoguang; Zheng, Xiao; Yang, Jinlong

2017-10-01

The manipulation of spin states at the molecular scale is of fundamental importance for the development of molecular spintronic devices. One of the feasible approaches for the modification of a molecular spin state is through the adsorption of certain specific atoms or molecules including H, NO, CO, NH3, and O2. In this paper, we demonstrate that the local spin state of an individual iron phthalocyanine (FePc) molecule adsorbed on an Au(111) surface exhibits controllable switching by hydrogen adsorption, as evidenced by using first-principles calculations based on density functional theory. Our theoretical calculations indicate that different numbers of hydrogen adsorbed at the pyridinic N sites of the FePc molecule largely modify the structural and electronic properties of the FePc/Au(111) composite by forming extra N-H bonds. In particular, the adsorption of one or up to three hydrogen atoms induces a redistribution of charge (spin) density within the FePc molecule, and hence a switching to a low spin state (S = 1/2) from an intermediate spin state (S = 1) is achieved, while the adsorption of four hydrogen atoms distorts the molecular conformation by increasing Fe-N bond lengths in FePc and thus breaks the ligand field exerted on the Fe 3d orbitals via stronger hybridization with the substrate, leading to an opposite switching to a high-spin state (S = 2). These findings obtained from the theoretical simulations could be useful for experimental manipulation or design of single-molecule spintronic devices.

Hydrogen isotope fractionation in methane plasma

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petitpas, G; Benard, P; Klebanoff, L E

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, clarifyingmore » 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.« less

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Ming; Kang, Zhan, E-mail: zhankang@dlut.edu.cn; 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-networkmore » (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.« less

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.

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

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2016-01-01

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

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

PubMed

Coplen, Tyler B; Qi, Haiping

2016-09-01

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

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

PubMed

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

2016-01-01

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

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.

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

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.

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.

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).

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.

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

Treesearch

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

2002-01-01

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

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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.

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.

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.

Unexpected hydrogen isotope variation in oceanic pelagic seabirds

USGS Publications Warehouse

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

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.

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.

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

PubMed

Kowalczyk, Piotr; MacElroy, J M D

2006-08-03

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

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).

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.

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.

Modeling Issues and Results for Hydrogen Isotopes in NIF Materials

NASA Astrophysics Data System (ADS)

Grossman, Arthur A.; Doerner, R. P.; Luckhardt, S. C.; Seraydarian, R.; Sze, D.; Burnham, A.

1998-11-01

The TMAP4 (G. Longhurst, et al. INEL 1992) model of hydrogen isotope transport in solid materials includes a particle diffusion calculation with Fick's Law modified for Soret Effect (Thermal Diffusion or Thermomigration), coupled to heat transport calculations which are needed because of the strong temperature dependence of diffusivity. These TMAP4 calculations applied to NIF show that high temperatures approaching the melting point and strong thermal gradients of 10^6 K/cm are reached in the first micron of wall material during the SXR pulse. These strong thermal gradients can drive hydrogen isotope migration up or down the thermal gradient depending on the sign of the heat of transport (Soret coefficient) which depends on whether the material dissolves hydrogen endothermically or exothermically. Two candidates for NIF wall material-boron carbide and stainless steel are compared. Boron carbide dissolves hydrogen exothermically so it may drive Soret migration down the thermal gradient deeper into the material, although the thermal gradient is not as large and hydrogen is not as mobile as in stainless steel. Stainless steel dissolves hydrogen endothermically, with a negative Soret coefficient which can drive hydrogen up the thermal gradient and out of the wall.

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.

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.

The effect of aluminum and platinum additives on hydrogen adsorption on mesoporous silicates

DOE PAGES

Melaet, Gérôme; Stavila, Vitalie; Klebanoff, Lennie; ...

2018-01-01

Recent theoretical predictions indicate that functional groups and additives could have a favorable impact on the hydrogen adsorption characteristics of sorbents; however, no definite evidence has been obtained to date and little is known about the impact of such modifications on the thermodynamics of hydrogen uptake and overall capacity.

The effect of aluminum and platinum additives on hydrogen adsorption on mesoporous silicates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melaet, Gérôme; Stavila, Vitalie; Klebanoff, Lennie

Recent theoretical predictions indicate that functional groups and additives could have a favorable impact on the hydrogen adsorption characteristics of sorbents; however, no definite evidence has been obtained to date and little is known about the impact of such modifications on the thermodynamics of hydrogen uptake and overall capacity.

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.

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.

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.

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

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.

Changes in hydrogen isotope ratios in sequential plumage stages: an implication for the creation of isotope-base maps for tracking migratory birds.

PubMed

Duxbury, J M; Holroyd, G L; Muehlenbachs, K

2003-09-01

Accurate reference maps are important in the use of stable-isotopes to track the movements of migratory birds. Reference maps created by the analysis of samples collected from young at the nest site are more accurate than simply referring to naturally occurring patterns of hydrogen isotope ratios created by precipitation cycles. Ratios of hydrogen isotopes in the nutrients incorporated early in the development of young birds can be derived from endogenous, maternal sources. Base-maps should be created with the analysis of tissue samples from hatchlings after local the isotopic signature of exogenous nutrients is dominant. Migratory species such as Peregrine Falcons are known to use endogenous sources in the creation of their eggs, therefore knowledge of what plumage stage best represents the local hydrogen ratios would assist in the planning of nest visits. We conducted diet manipulation experiments involving Japanese Quail and Peregrine Falcons to determine the plumage stage when hydrogen isotope ratios were indicative of a switch in their food source. The natal down of both the quail and falcons reflected the diet of breeding adult females. The hydrogen isotope ratios of a new food source were dominant in the juvenile down of the young falcons, although a further shift was detected in the final juvenile plumage. The juvenile plumage is grown during weeks 3-4 after hatch on Peregrine Falcons. Nest visits for the purpose of collecting feathers for isotope-base-map creation should be made around 4 weeks after the presumed hatch of the young falcons.

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.

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.

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).

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

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.

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 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<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 D2O indicate

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

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

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.

Equilibrium carbon and hydrogen isotope fractionation in iron

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2009-12-01

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

Synthesis of methanol from CO2 hydrogenation promoted by dissociative adsorption of hydrogen on a Ga3Ni5(221) surface.

PubMed

Tang, Qingli; Shen, Zhemin; Huang, Liang; He, Ting; Adidharma, Hertanto; Russell, Armistead G; Fan, Maohong

2017-07-19

Catalytic carbon dioxide (CO 2 ) hydrogenation to liquid fuels including methanol (CH 3 OH) has attracted great attention in recent years. In this work, density functional theory (DFT) calculations have been employed to study the reaction mechanisms of CO 2 hydrogenation to CH 3 OH on Ga 3 Ni 5 (221) surfaces. The results show that all intermediates except for the O atom prefer to adsorb on Ni sites, and dissociative adsorption of hydrogen (H 2 ) on the Ga 3 Ni 5 (221) surface is almost barrierless and highly exothermic, favoring CO 2 hydrogenation. Moreover, the presence of Ga indeed enhances the dissociative adsorption of H 2 , and this is verified by the projected density of states (PDOS) analysis. Importantly, three possible reaction pathways based on formate (HCOO) and hydrocarboxyl (COOH) formations and reverse water gas shift (rWGS) with carbon monoxide (CO) hydrogenation have been discussed. It is found that CO 2 reduction to CH 3 OH in these pathways prefers to occur entirely via the Langmuir-Hinshelwood (L-H) mechanism. COOH generation is the most favorable pathway because the HCOO and rWGS with CO hydrogenation pathways have high energy barriers and the resulting HCOOH intermediate in the HCOO pathway is unstable. In the COOH reaction pathway, CO 2 is firstly hydrogenated to trans-COOH, followed by the formation of COH via three isomers of COHOH, its hydrogenation to trans-HCOH, and then the production of CH 3 OH via a CH 2 OH intermediate.

Simulation of hydrogen adsorption systems adopting the flow through cooling concept

DOE PAGES

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

2014-10-13

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

A Hydrogen and He Isotope Nanoprobe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doyle, Barney L.; Van Deusen, Stuart B.

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

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.

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

PubMed Central

Sharma, Sudhir C.; Klinman, Judith P.

2009-01-01

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

Direct observation and modelling of ordered hydrogen adsorption and catalyzed ortho-para conversion on ETS-10 titanosilicate material.

PubMed

Ricchiardi, Gabriele; Vitillo, Jenny G; Cocina, Donato; Gribov, Evgueni N; Zecchina, Adriano

2007-06-07

Hydrogen physisorption on porous high surface materials is investigated for the purpose of hydrogen storage and hydrogen separation, because of its simplicity and intrinsic reversibility. For these purposes, the understanding of the binding of dihydrogen to materials, of the structure of the adsorbed phase and of the ortho-para conversion during thermal and pressure cycles are crucial for the development of new hydrogen adsorbents. We report the direct observation by IR spectroscopic methods of structured hydrogen adsorption on a porous titanosilicate (ETS-10), with resolution of the kinetics of the ortho-para transition, and an interpretation of the structure of the adsorbed phase based on classical atomistic simulations. Distinct infrared signals of o- and p-H2 in different adsorbed states are measured, and the conversion of o- to p-H2 is monitored over a timescale of hours, indicating the presence of a catalyzed reaction. Hydrogen adsorption occurs in three different regimes characterized by well separated IR manifestations: at low pressures ordered 1:1 adducts with Na and K ions exposed in the channels of the material are formed, which gradually convert into ordered 2:1 adducts. Further addition of H2 occurs only through the formation of a disordered condensed phase. The binding enthalpy of the Na+-H2 1:1 adduct is of -8.7+/-0.1 kJ mol(-1), as measured spectroscopically. Modeling of the weak interaction of H2 with the materials requires an accurate force field with a precise description of both dispersion and electrostatics. A novel three body force field for molecular hydrogen is presented, based on the fitting of an accurate PES for the H2-H2 interaction to the experimental dipole polarizability and quadrupole moment. Molecular mechanics simulations of hydrogen adsorption at different coverages confirm the three regimes of adsorption and the structure of the adsorbed phase.

Hydrogen isotope exchange in a metal hydride tube

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, David B.

2014-09-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Optimization Study of Hydrogen Gas Adsorption on Zig-zag Single-walled Carbon Nanotubes: The Artificial Neural Network Analysis

NASA Astrophysics Data System (ADS)

Nasruddin; Lestari, M.; Supriyadi; Sholahudin

2018-03-01

The use of hydrogen gas in fuel cell technology has a huge opportunity to be applied in upcoming vehicle technology. One of the most important problems in fuel cell technology is the hydrogen storage. The adsorption of hydrogen in carbon-based materials attracts a lot of attention because of its reliability. This study investigated the adsorption of hydrogen gas in Single-walled Carbon Nano Tubes (SWCNT) with chilarity of (0, 12), (0, 15), and (0, 18) to find the optimum chilarity. Artificial Neural Networks (ANN) can be used to predict the hydrogen storage capacity at different pressure and temperature conditions appropriately, using simulated series of data. The Artificial Neural Network is modeled as a predictor of the hydrogen adsorption capacity which provides solutions to some deficiencies in molecular dynamics (MD) simulations. In a previous study, ANN configurations have been developed for 77k, 233k, and 298k temperatures in hydrogen gas storage. To prepare this prediction, ANN is modeled to find out the configurations that exist in the set of training and validation of specified data selection, the distance between data, and the number of neurons that produce the smallest error. This configuration is needed to make an accurate artificial neural network. The configuration of neural network was then applied to this research. The neural network analysis results show that the best configuration of artificial neural network in hydrogen storage is at 233K temperature i.e. on SWCNT with chilarity of (0.12).

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.

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.

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

PubMed Central

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

1999-01-01

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

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.

Joint adsorption of light hydrogen by CuO and 5A molecular sieves

NASA Astrophysics Data System (ADS)

Wang, J.; Zhan, Y.; Wang, W.; Wang, R. S.

2018-03-01

H2 is the primary cause of the deteriorating vacuum degree of high-vacuum multilayer insulation tank (HVMLIT). At present, the precious metal PdO is used to adsorb H2 and maintain the high vacuum of HVMLIT. In this study, CA, a compound hydrogen adsorbent integrated with the cheap metal CuO and 5A molecular sieves, is adopted to jointly adsorb light hydrogen in HVMLIT. This work also investigates the adsorption characteristics and mechanisms of CA.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu Miaomiao; Sun Qiang; Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284

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 atomsmore » 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.« less

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.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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.

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

NASA Astrophysics Data System (ADS)

Keppler, Frank; Bahlmann, Enno; Greule, Markus; Schöler, Heinz Friedrich; Wittmer, Julian; Zetzsch, Cornelius

2018-05-01

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

Hydrogen adsorption strength and sites in the metal organic framework MOF5: Comparing experiment and model calculations

NASA Astrophysics Data System (ADS)

Mulder, F. M.; Dingemans, T. J.; Schimmel, H. G.; Ramirez-Cuesta, A. J.; Kearley, G. J.

2008-07-01

Hydrogen adsorption in porous, high surface area, and stable metal organic frameworks (MOF's) appears a novel route towards hydrogen storage materials [N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, O.M. Yaghi, Science 300 (2003) 1127; J.L.C. Rowsell, A.R. Millward, K. Sung Park, O.M. Yaghi, J. Am. Chem. Soc. 126 (2004) 5666; G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guegan, Chem. Commun. (2003) 2976; T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Férey, Chem. Eur. J. 10 (2004) 1373]. A prerequisite for such materials is sufficient adsorption interaction strength for hydrogen adsorbed on the adsorption sites of the material because this facilitates successful operation under moderate temperature and pressure conditions. Here we report detailed information on the geometry of the hydrogen adsorption sites, based on the analysis of inelastic neutron spectroscopy (INS). The adsorption energies for the metal organic framework MOF5 equal about 800 K for part of the different sites, which is significantly higher than for nanoporous carbon materials (˜550 K) [H.G. Schimmel, G.J. Kearley, M.G. Nijkamp, C.T. Visser, K.P. de Jong, F.M. Mulder, Chem. Eur. J. 9 (2003) 4764], and is in agreement with what is found in first principles calculations [T. Sagara, J. Klassen, E. Ganz, J. Chem. Phys. 121 (2004) 12543; F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113]. Assignments of the INS spectra is realized using comparison with independently published model calculations [F.M. Mulder, T.J. Dingemans, M. Wagemaker, G.J. Kearley, Chem. Phys. 317 (2005) 113] and structural data [T. Yildirim, M.R. Hartman, Phys. Rev. Lett. 95 (2005) 215504].

Comparable hydrogen isotopic fractionation of plant leaf wax n-alkanoic acids in arid and humid subtropical ecosystems

NASA Astrophysics Data System (ADS)

Gao, Li; Zheng, Mei; Fraser, Matthew; Huang, Yongsong

2014-02-01

Leaf wax hydrogen isotope proxies have been widely used to reconstruct past hydrological changes. However, published reconstructions have given little consideration for the potentially variable hydrogen isotopic fractionation relative to precipitation (ɛwax-p) under different climate and environmental settings. Chief among various potential factors controlling fractionation is relative humidity, which is known to strongly affect oxygen isotopic ratios of plant cellulose, but its effect on hydrogen isotopic fractionation of leaf waxes is still ambiguous. Analyses of lake surface sediments and individual modern plants have provided valuable information on the variability of ɛwax-p, but both approaches have significant limitations. Here, we present an alternative method to obtain the integrated, time-resolved ecosystem-level ɛwax-p values, by analyzing modern aerosol samples collected weekly from arid (Arizona lowlands) and humid subtropical (Atlanta, Georgia) environments during the main growth season. Because aerosol samples mainly reflect regional leaf wax resources, the extreme contrast in the hydroclimate and associated vegetation assemblages between our study sites allows us to rigorously assess the impact of relative humidity and associated vegetation assemblages on leaf wax hydrogen isotopic fractionation. We show there is only minor difference (mostly <10‰) in the mean ɛwax-p values in the two end-member environments. One possible explanation is that the positive isotopic effects of low relative humidity are offset by progressive replacement of trees with grasses that have a more negative apparent fractionation. Our results represent an important step toward quantitative interpretation of leaf wax hydrogen isotopic records.

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

USGS Publications Warehouse

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

2015-01-01

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

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.

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

PubMed

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

2009-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Benzene Adsorption - A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions

DOE PAGES

Gonzales, Ivana; Chung, Hoon Taek; Kim, Yu Seung

2017-09-25

Slow hydrogen oxidation reaction (HOR) kinetics on Pt under alkaline conditions is a significant technical barrier for the development of high-performance hydroxide exchange membrane fuel cells. Here we report that benzene adsorption on Pt is a major factor responsible for the sluggish HOR. Furthermore, we demonstrate that bimetallic catalysts, such as PtMo/C, PtNi/C, and PtRu/C, can reduce the adsorption of benzene and thereby improve HOR activity. In particular, the HOR voltammogram of PtRu/C in 0.1 M benzyl ammonium showed minimal benzene adsorption. Density functional theory calculations indicate that the adsorption of benzyl ammonium on the bimetallic PtRu is endergonic formore » all four possible orientations of the cation, which explains the significantly better HOR activity observed for the bimetallic catalysts. In conclusion, the new HOR inhibition mechanism described here provides insights for the design of future polymer electrolytes and electrocatalysts for better-performing polymer membrane-based fuel cells.« less

First principles study of hydrogen adsorption on carbon nanowires.

NASA Astrophysics Data System (ADS)

Tapia, Alejandro; Aguilera, Luis; Murrieta, Gabriel; de Coss, Romeo

2007-03-01

Recently has been reported a new type of one-dimensional carbon structures. Carbon nanowires formed by a linear carbon-atom chain inside an armchair (5,5) carbon nanotube has been observed using high-resolution transmission electron microscopy. In the present work we have studied the changes in the electronic structure of a carbon nanowires and (5,5) single-walled carbon nanotubes (SWCN) when a hydrogen atom is adsorbed. We used the Density Functional Theory and the calculations where performed by the pseudopotentials LCAO method (SIESTA code) and the Generalized Gradient Approximation (GGA) for the exchange-correlation potential. We have analyzed the changes in the atomic structure, density of states (LDOS), and the local orbital population. We found charge transfer from the nanotube to the linear chain and the hydrogen atom, the electronic character of the chain and nanotube sub-systems in chain@SWCN is the same that in the corresponding isolated systems, chain or SWCN. But the hydrogen adsorption produced changes in the atomic estructure and the electronic properties. This research was supported by PRIORI-UADY under Grant No. FING-05-004 and Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grants No. 43830-F and 49985-J.

The hydrogen isotope ratio in W7-AS during deuterium NBI heating

NASA Astrophysics Data System (ADS)

Zebisch, P.; Taglauer, E.; W7-AS Team; NBI Team

1999-04-01

With a so-called sniffer probe the fraction of hydrogen during discharges with deuterium NBI heating was studied in the plasma edge of the stellarator W7-AS. As expected, the ratios were significantly lower than in discharges with hydrogen NBI heating but were higher than those in discharges with only ECRH. An examination of the possible reasons for this increase concludes that it is not only partially caused by the direct influence of neutral injection but also depends on the energy content of the plasma determined by the heating power and the confinement time. Of course, the isotope ratio also depends on the starting conditions, i.e. the isotope ratio before the onset of NBI.

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes

NASA Astrophysics Data System (ADS)

Mazzuca, James W.; Haut, Nathaniel K.

2018-06-01

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes.

PubMed

Mazzuca, James W; Haut, Nathaniel K

2018-06-14

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bak, J. H.; Le, V. D.; Kang, J.

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.more » 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.« less

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

PubMed

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

2014-06-15

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

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

PubMed

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

2009-05-20

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

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

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

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.

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.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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,more » 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.« less

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

PubMed

Bong, Yeon-Sik; Lee, Kwang-Sik; Shin, Woo-Jin; Ryu, Jong-Sik

2008-09-01

We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation. Copyright (c) 2008 John Wiley & Sons, Ltd.

Hydrogen isotopes transport parameters in fusion reactor materials

NASA Astrophysics Data System (ADS)

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

1998-06-01

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

Stable hydrogen isotope analysis of bat hair as evidence for seasonal molt and long-distance migration

USGS Publications Warehouse

Cryan, P.M.; Bogan, M.A.; Rye, R.O.; Landis, G.P.; Kester, C.L.

2004-01-01

Although hoary bats (Lasiurus cinereus) are presumed to be migratory and capable of long-distance dispersal, traditional marking techniques have failed to provide direct evidence of migratory movements by individuals. We measured the stable hydrogen isotope ratios of bat hair (δDh) and determined how these values relate to stable hydrogen isotope ratios of precipitation (δDp). Our results indicate that the major assumptions of stable isotope migration studies hold true for hoary bats and that the methodology provides a viable means of determining their migratory movements. We present evidence that a single annual molt occurs in L. cinereus prior to migration and that there is a strong relationship between δDh and δDp during the molt period. This presumably reflects the incorporation of local δDp into newly grown hair. Furthermore, we present evidence that individual hoary bats are capable of traveling distances in excess of 2,000 km and that hair is grown at a wide range of latitudes and elevations. Stable hydrogen isotope analysis offers a promising new tool for the study of bat migration.

Hydrogen Isotope Geochemistry of Mariana Trough Lavas

NASA Astrophysics Data System (ADS)

Oleary, J.; Kitchen, N.; Eiler, J.

2002-12-01

Basaltic lavas from the Marianas trough vary in water content from values similar to mid-ocean ridge basalts (MORBs) to ten times those values. These variations plausibly reflect addition of subducted water to the mantle wedge, but must also reflect variations in extent of melting and crystallization-differentiation. We report hydrogen isotope data for 18 samples of lavas from the Mariana trough; these measurements, when combined with other geochemical data, constrain the relative proportions of subducted vs. 'primitive' water in their mantle sources. Previous measurements of the hydrogen isotope composition of Mariana trough lavas [1] found a correlation between dD and measured water content, consistent with two-component mixing between water in the ambient MORB source and water from the subducted slab, but include only four samples, only two of which have known major and minor element geochemistry. Our purpose is to confirm this result and expand it to include a more representative sampling. Our measurements made use of a recently developed technique for on-line stepped heating, water reduction and hydrogen isotope mass spectrometry [2]. This method is appropriate for relatively small samples of basaltic glass (ca. 100 μg to 1 mg) and up to 10 analyses can be performed per day. Its principle advantages for our purposes are that it can be applied to even small or glass-poor samples and it is fast enough to permit replication of all data and analysis of relatively large numbers of standards. Hydrogen isotope compositions of Mariana trough lavas vary between -74 per mil and -34 per mil (SMOW); this compares with a range of -46 to -32 per mil for related lavas in [1] and is similar to the previously observed range for back-arc-basin basalts generally (-70 to -32 per mil). Two-thirds of our sample suite span a small range in dD (-40+/-4 ). We suggest this average is the most representative value for back arc basin basalts measured to-date. Our data are inconsistent

Adsorption of 2 Chloroethyl Ethyl Sulfide on Silica: Binding Mechanism and Energy of a Bifunctional Hydrogen-Bond Acceptor at the Gas Surface Interface

DTIC Science & Technology

2014-11-19

C. A. S.; Sumpter, K. B.; Wagner, G. W.; Rice, J. S. Degradation of the Blister Agent Sulfur Mustard, Bis(2-chloroethyl) Sulfide, on Concrete . J...SECURITY CLASSIFICATION OF: This work investigates the fundamental nature of sulfur mustard surface adsorption by characterizing interfacial hydrogen...nature of sulfur mustard surface adsorption by characterizing interfacial hydrogen bonding and other intermolecular forces for the surrogate molecule

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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)

Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

NASA Astrophysics Data System (ADS)

Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

2017-08-01

Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

Compound-Specific Hydrogen Isotopic Records of Holocene Climate Dynamics in the Northeastern U.S.

NASA Astrophysics Data System (ADS)

Stefanescu, I.; Shuman, B. N.

2017-12-01

The northeastern United States, located between the location of Laurentide ice sheet and the dynamic North Atlantic Ocean, is an ideal region for studying paleoclimate changes on centennial to multi-millennial time scales because the region experienced multiple abrupt climate changes and variations over the past 14 ka. Over the Holocene, the region's long-term climate trend was influenced by isolation changes, the retreat of the Laurentide Ice Sheet (LIS), changes in atmospheric composition and changes in the North Atlantic Meridional Overturning Circulation (AMOC). Hydrological and pollen records show that multiple abrupt climate changes punctuate the long-term trends, even after the widely recognized events associated with the LIS and AMOC, but the mechanisms behind the abrupt climate changes observed are not well understood. To understand the mechanisms behind abrupt climate shifts, their impact on hydrology, ecosystems, regional and local climates, additional insights are needed. Compound-specific hydrogen isotope (D/H) ratios derived from terrestrial and aquatic leaf waxes and preserved in lake sediments, have been shown to record D/H ratios of environmental water and we use such data to further investigate the regional climate history. Here we present hydrogen isotope records of precipitation using compound specific hydrogen isotope of leaf wax n-alkanes derived from aquatic and terrestrial leaf waxes from three lakes: Twin Ponds, Vermont; Blanding Pond, Pennsylvania; and Crooked Pond, Massachusetts. We use the results to evaluate common climate trends across the region from an isotopic perspective and to assess changes in the spatial isotopic gradients across the northeastern US during the Holocene.

Effect of Hydrogen Adsorption on the Stone-Wales Transformation in Small-Diameter Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Openov, L. A.; Podlivaev, A. I.

2018-04-01

The effect of hydrogenation of (4, 0) and (3, 0) carbon nanotubes on the Stone-Wales transformation is studied in the framework of the nonorthogonal tight-binding model. It is shown that the atomic hydrogen adsorption can lead to both a decrease and an increase in the barriers for the direct and inverse transformations depending on the orientation of a rotating C-C bond with respect to the nanotube axis. The characteristic times of formation and annealing the Stone-Wales defects have been estimated. The Young's moduli have been calculated.

Factors influencing the turnover and net isotopic discrimination of hydrogen isotopes in proteinaceous tissue: experimental results using Japanese quail.

PubMed

Storm-Suke, Andrea; Norris, D Ryan; Wassenaar, Leonard I; Chin, Eunice; Nol, Erica

2012-01-01

Stable hydrogen isotopes (δ(2)H) are commonly used in studies of animal movement. Tissue that is metabolically inactive after growth (e.g., feathers) provides spatial or dietary information that reflects only the period of tissue growth, whereas tissues that are metabolically active (e.g., red blood cells) provide a moving window of forensic information. However, using δ(2)H for studies of animal movement relies on the assumption that tissue δ(2)H values reflect dietary δ(2)H values, plus or minus a net diet-tissue discrimination value, and that the turnover rate is known for metabolically active tissue. The metabolic rate of an animal may influence both diet-tissue discrimination values and isotopic tissue turnover rate, but this hypothesis has not been tested experimentally. To examine the metabolic hypothesis, an experimental group of 12 male and 15 female captive Japanese quail (Coturnix japonica) was housed at 8.9°C for 90 d to elevate their metabolic rates (mL CO(2) min(-1)), and a control group of 12 male and 13 female quail was housed at room temperature during the same period. For both experimental and control birds, diet-tissue discrimination values were estimated for red blood cells and feathers. To determine turnover rate, experimental and control birds were switched from a (2)H-enriched diet to a (2)H-depleted diet, with red blood cells sampled before and after diet switch. Metabolic rate did not influence red blood cell hydrogen isotope turnover rate (η(2)(p) = 0.24)) or diet-feather isotope discrimination values (η(2)(p) = 0.86). Diet-feather hydrogen isotopic discrimination had a significant sex plus treatment interaction effect; female feathers were depleted in (2)H relative to food regardless of treatment, whereas male feathers were enriched in (2)H. The effect of sex suggested that experimental studies should examine whether coeval males and females differ in blood δ(2)H levels during certain periods of the annual cycle.

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study

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

NASA Astrophysics Data System (ADS)

Mohajeri, Afshan; Dashti, Nasimeh Lari

2017-06-01

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

Adsorption configurations and scanning voltage determined STM images of small hydrogen clusters on bilayer graphene.

PubMed

Cao, Teng Fei; Huang, Liang Feng; Zheng, Xiao Hong; Zhou, Wang Huai; Zeng, Zhi

2013-11-21

By density functional theory calculations, the scanning tunneling microscopy (STM) images of various hydrogen clusters adsorbed on bilayer-graphene are systematically simulated. The hydrogen configurations of the STM images observed in the experiments have been thoroughly figured out. In particular, two kinds of hydrogen dimers (ortho-dimer, para-dimer) and two kinds of tetramers (tetramer-A, -B) are determined to be the hydrogen configurations corresponding to the ellipsoidal-like STM images with different structures and sizes. One particular hexamer (hexamer-B) is the hydrogen configuration generating the star-like STM images. For each hydrogen cluster, the simulated STM images show unique voltage-dependent features, which provides a feasible way to determine hydrogen adsorption states on graphene or graphite surface in the experiments by varying-voltage measurements. Stability analysis proves that the above determined hydrogen configurations are quite stable on graphene, hence they are likely to be detected in the STM experiments. Consequently, through systematic analysis of the STM images and the stability of hydrogen clusters on bilayer graphene, many experimental observations have been consistently explained.

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Brady D.; Moran, James J.; Nims, Megan K.

Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

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. "

A DFT+U investigation of hydrogen adsorption on the LaFeO3(010) surface.

PubMed

Boateng, Isaac W; Tia, Richard; Adei, Evans; Dzade, Nelson Y; Catlow, C Richard A; de Leeuw, Nora H

2017-03-08

The ABO 3 perovskite lanthanum ferrite (LaFeO 3 ) is a technologically important electrode material for nickel-metal hydride batteries, energy storage and catalysis. However, the electrochemical hydrogen adsorption mechanism on LaFeO 3 surfaces remains under debate. In the present study, we have employed spin-polarized density functional theory calculations, with the Hubbard U correction (DFT+U), to unravel the adsorption mechanism of H 2 on the LaFeO 3 (010) surface. We show from our calculated adsorption energies that the preferred site for H 2 adsorption is the Fe-O bridge site, with an adsorption energy of -1.18 eV (including the zero point energy), which resulted in the formation of FeOH and FeH surface species. H 2 adsorption at the surface oxygen resulted in the formation of a water molecule, which leaves the surface to create an oxygen vacancy. The H 2 molecule is found to interact weakly with the Fe and La sites, where it is only physisorbed. The electronic structures of the surface-adsorption systems are discussed via projected density of state and Löwdin population analyses. The implications of the calculated adsorption strengths and structures are discussed in terms of the improved design of nickel-metal hydride (Ni-MH) battery prototypes based on LaFeO 3 .

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.

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.

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

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.

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.

A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

NASA Astrophysics Data System (ADS)

Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Flemming, Roberta L.; Rossman, George R.; Eiler, John M.; Neal, Clive R.; Osinski, Gordon R.

2017-09-01

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth-Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from -280 to + 310 ‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about - 280 ‰, evolving to about + 310 ‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

[Temporal and spatial variations of hydrogen and oxygen isotopes in Tuojia River and its influencing factors.

PubMed

Wu, Hong Bao; Zhao, Qiang; Qin, Xiao Bo; Gao, Qing Zhu; Lyu, Cheng Wen

2018-05-01

The characteristics of hydrogen and oxygen stable isotopes in river is important for regional hydrologic cycle research. To uncover water supply sources in subtropical agricultural basin from a perspective of stable isotopes, field measurements were conducted in four reaches (S 1 , S 2 , S 3 and S 4 ) of Tuojia River from April to August 2017. We analyzed the spatial and temporal variations in hydrogen and oxygen isotopes and deuterium excess parameters and their relationship with precipitation, altitude and water quality. Results showed that hydrogen and oxygen isotopes and deuterium excess values ranged from -43.17‰ to -26.43‰ (-35.50‰±5.44‰), -7.94‰ to -5.70‰ (-6.86‰±0.74‰), and 16.77‰ to 23.49‰ (19.39‰±1.95‰), respectively. Under the influence of monsoon circulation, hydrogen and oxygen isotopes showed substantial seasonal variation, with spring (δD: -29.88‰±3.31‰; δ 18 O: -6.18‰±0.57‰) > summer (δD: -39.25‰±2.65‰; δ 18 O: -7.32‰±0.42‰). The spatial distribution of hydrogen and oxygen isotopes values increased fluctuantly with the position from the sampling site to the river's source, with δD: S 1 ＜S 4 ＜S 3 ＜S 2 , and δ 18 O: S 1 ＜S 3 ＜S 4 ＜S 2 . The deuterium excess values had no significant temporal variation, while it spatially increased gradually with the river levels. The slope and intercept of water line in this river were smaller than that of the local meteoric water line, suggesting that precipitation was the primary water source for this river. At the seasonal scale, both δD and δ 18 O were significantly negatively correlated with water temperature (δD: r=-0.92; δ 18 O: r=-0.88) and δ 18 O was negatively correlated with altitude (r=-0.96). At spatial scale, δ 18 O had a significantly positive correlation with water temperature. The δD and δ 18 O had negative correlation with precipitation, but being not statistically significant.

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

Treesearch

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

2009-01-01

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

Dynamic Cooperation of Hydrogen Binding and π Stacking in ssDNA Adsorption on Graphene Oxide.

PubMed

Xu, Zhen; Lei, Xiaoling; Tu, Yusong; Tan, Zhi-Jie; Song, Bo; Fang, Haiping

2017-09-21

Functional nanoscale structures consisting of a DNA molecule coupled to graphene or graphene oxide (GO) have great potential for applications in biosensors, biomedicine, nanotechnology, and materials science. Extensive studies using the most sophisticated experimental techniques and theoretical methods have still not clarified the dynamic process of single-stranded DNA (ssDNA) adsorbed on GO surfaces. Based on a molecular dynamics simulation, this work shows that an ssDNA segment could be stably adsorbed on a GO surface through hydrogen bonding and π-π stacking interactions, with preferential binding to the oxidized rather than to the unoxidized region of the GO surface. The adsorption process shows a dynamic cooperation adsorption behavior; the ssDNA segment first captures the oxidized groups of the GO surface by hydrogen bonding interaction, and then the configuration relaxes to maximize the π-π stacking interactions between the aromatic rings of the nucleobases and those of the GO surface. We attributed this behavior to the faster forming hydrogen bonding interaction compared to π-π stacking; the π-π stacking interaction needs more relaxation time to regulate the configuration of the ssDNA segment to fit the aromatic rings on the GO surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Development of Hydrogen Isotope Extraction Technologies for a Full LiMIT-Style PFC Liquid Lithium Loop

NASA Astrophysics Data System (ADS)

Christenson, Michael; Szott, Matthew; Stemmley, Steven; Mettler, Jeremy; Wendeborn, John; Moynihan, Cody; Ahn, Chisung; Andruczyk, Daniel; Ruzic, David

2017-10-01

Lithium has proven over numerous studies to improve core confinement, allowing access to operational regimes previously unattainable when using solid, high-Z divertor and limiter modules in magnetic confinement devices. Lithium readily absorbs fuel species, and while this is advantageous, it is also detrimental with regards to tritium inventory and safety concerns. As such, extraction technologies for the recovery of hydrogenic isotopes captured by lithium require development and testing in the context of a larger lithium loop recycling system. Proposed reclamation technologies at the University of Illinois at Urbana-Champaign (UIUC) will take advantage of the thermophysical properties of the lithium-hydrogen-lithium hydride system as the driving force for recovery. Previous work done at UIUC indicates that hydrogen release from pure lithium hydride reaches a maximum of 7 x 1018 s-1 at 665 °C. While this recovery rate is appreciable, reactor-scale scenarios will require isotope recycling to happen on an even faster timescale. The ratio of isotope dissolution to hydride precipitate formation must therefore be determined, along with the energy needed to recoup trapped hydrogen isotopes. Extraction technologies for use with a LiMIT-style loop system will be discussed and results will be presented. DOE/ALPS DE-FG02-99ER54515.

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

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

Hydrogen adsorption site on the Ni?110?-p(1 × 2)-H surface from time-of-flight scattering and recoiling spectrometry (TOF-SARS)

NASA Astrophysics Data System (ADS)

Bu, H.; Roux, C. D.; Rabalais, J. W.

The adsorption site of hydrogen on the Ni{110}-p(1 × 2)-H surface resulting from saturation exposure to H 2 at ˜ 310-350 K has been investigated by time-of-flight scattering and recoiling spectrometry (TOF-SARS). The recoiled neutral plus ion hydrogen atom flux resulting from 2-5 keV Ar + or Ne + pulsed ion beams incident on the surface was monitored as a function of crystal azimuthal angle and beam incidence angle. From classical trajectory calculations and shadowing and blocking analyses, it is concluded that hydrogen atoms are localized at the pseudo-three-fold sites on the (1 × 2) missing-row (MR) reconstructed Ni{110} surface; the (1 × 2) MR reconstruction is induced by hydrogen adsorption shown elsewhere [Surf. Sci. 259 (1991) 253]. Only the pseudo-three-fold site is consistent with all of the experimental data. The coordinates of the hydrogen adsorption site with respect to the nickel lattice were determined. The lateral distance of hydrogen from the 1st-layer Ni <1 overline10> rows is 1.56 ± 0.12 Å and the vertical distance above the substrate is 0.21 ± 0.12 Å, providing NiH bond lengths of 2.0 Å to the two-layer Ni atoms and 1.5 Å to the 2nd-layer Ni atom.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1989-12-01

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

Strong coupling effects in the polarized IR spectra of the chain hydrogen bond systems in imidazole crystals: H/D isotopic ?self-organization? effects in the IR spectra of isotopically diluted imidazole single crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Michta, Anna

2004-11-01

This paper presents the investigation results of the polarized IR spectra of H1245 imidazole crystals and of D1H245, D1245 and H1D245 imidazole deuterium derivative crystals. The spectra were measured using polarized light at the room temperature and at 77 K by a transmission method, for two different crystalline faces. Theoretical analysis of the results concerned linear dichroic effects, H/D isotopic and temperature effects, observed in the spectra of the hydrogen and of the deuterium bonds in imidazole crystals, at the frequency ranges of νN-H and νN-D bands. The basic crystal spectral properties can be satisfactorily interpreted in a quantitative way for a hydrogen bond linear dimer model. Such a model explains not only a two-branch structure of the νN-H and νN-D bands in crystalline spectra, but also some essential linear dichroic effects in the band frequency ranges, for isotopically diluted crystals. Model calculations, performed within the limits of the strong-coupling model, allowed for quantitative interpretation and for understanding of the basic properties of the hydrogen bond IR spectra of imidazole crystals, H/D isotopic, temperature and dichroic effects included. The results allowed verification of theoretical models proposed recently for the imidazole crystal spectra generation mechanisms. In the scope of our studies, the mechanism of H/D isotopic self-organization processes, taking place in the crystal hydrogen bond lattices, was also recognized. It was proved that for isotopically diluted crystalline samples of imidazole, a non-random distribution of protons and deuterons exclusively occurs in some restricted fragments (domains) of open chains of the hydrogen-bonded molecules. Nevertheless, these co-operative interactions between the hydrogen bonds do not concern adjacent fragments of neighboring hydrogen bond chains in the lattice. Analysis of the isotopic self-organization effects in the spectra of imidazole crystals delivered crucial

Triple oxygen and hydrogen isotopes of gypsum hydration water for quantitative paleo-humidity reconstruction

NASA Astrophysics Data System (ADS)

Gázquez, Fernando; Morellón, Mario; Bauska, Thomas; Herwartz, Daniel; Surma, Jakub; Moreno, Ana; Staubwasser, Michael; Valero-Garcés, Blas; Delgado-Huertas, Antonio; Hodell, David A.

2018-01-01

Atmospheric relative humidity is an important parameter affecting vegetation yet paleo-humidity proxies are scarce and difficult to calibrate. Here we use triple oxygen (δ17O and δ18O) and hydrogen (δD) isotopes of structurally-bound gypsum hydration water (GHW) extracted from lacustrine gypsum to quantify past changes in atmospheric relative humidity. An evaporation isotope-mass-balance model is used together with Monte Carlo simulations to determine the range of climatological conditions that simultaneously satisfy the stable isotope results of GHW, and with statistically robust estimates of uncertainty. We apply this method to reconstruct the isotopic composition of paleo-waters of Lake Estanya (NE Spain) and changes in normalized atmospheric relative humidity (RHn) over the last glacial termination and Holocene (from ∼15 to 0.6 cal. kyrs BP). The isotopic record indicates the driest conditions occurred during the Younger Dryas (YD; ∼12-13 cal. kyrs BP). We estimate a RHn of ∼40-45% during the YD, which is ∼30-35% lower than today. Because of the southward displacement of the Polar Front to ∼42°N, it was both windier and drier during the YD than the Bølling-Allerød period and Holocene. Mean atmospheric moisture gradually increased from the Preboreal to Early Holocene (∼11 to 8 cal. kyrs BP, 50-60%), reaching 70-75% RHn from ∼7.5 cal. kyrs BP until present-day. We demonstrate that combining hydrogen and triple oxygen isotopes in GHW provides a powerful tool for quantitative estimates of past changes in relative humidity.

Spontaneous adsorption on a hydrophobic surface governed by hydrogen bonding.

PubMed

Dang, Fuquan; Hasegawa, Takeshi; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Kaji, Noritada; Yasui, Takao; Baba, Yoshinobu

2009-08-18

Spontaneous adsorption from solution onto solid surface is a common phenomenon in nature, but the force that governs adsorption is still a matter of considerable debate. (1, 2) We found that surfactants and cellulose adsorb from solution onto a poly(methyl methacrylate) (PMMA) surface in an ordered and cooperative way governed by hydrogen bonding. The glucose rings of n-dodecyl-beta-D-maltoside (DDM) and hydroxyethylcellulose (HEC) stand perpendicular to the surface, H-bond to the surface COOMe groups with their C=O and Me-O bonds parallel to the surface, and form a tight monolayer. The non-H-bonded COOMe groups orient their C=O bonds perpendicular to the surface. In contrast, the glucose rings of hydrophobically modified hydroxyethylcellulose (HMHEC) lie flat with the side chains perpendicular to the surface and H-bond to the perpendicular-oriented C=O groups. The non-H-bonded COOMe groups orient their C=O bonds parallel but Me-O bonds near-perpendicular to the surface for stabilizing HMHEC. The current work provides a detailed picture of how surface-active molecules interact with a solid surface and self-assemble into greatly different architectures.

Hydrogen sensor

DOEpatents

Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

2010-11-23

A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

[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.

Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature.

PubMed

Uemura, Kazuhiro; Yamasaki, Yukari; Onishi, Fumiaki; Kita, Hidetoshi; Ebihara, Masahiro

2010-11-01

A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ⊃ solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ⊃ solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ⊃ solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such

Polarization IR spectra of hydrogen bonded pyrazole crystals: self-organization effects in proton and deuteron mixture systems. Long-range H/D isotopic effects

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Machelska, Aleksandra

2002-02-01

This paper deals with experimental studies of the polarization IR spectra of solid-state pyrazole H1345, as well as of its H1D345, D1H345 and D1345 deuterium derivatives. Spectra were measured for the νNH and νND band frequency ranges at temperatures of 298 and 77 K. The spectra were found to strongly change their intensity distribution and their polarization properties with the decrease of temperature. These effects were ascribed to some temperature-induced conformational changes in the hydrogen bond lattices. The studies reported allowed the finding of new kind of isotopic effects H/D in the open-chain hydrogen bond systems, i.e. the self-organization effects. It was found that the spectrally active aggregates of hydrogen bonds remain unchanged despite the growing isotope H/D exchange rate. This statement was supported by analysis of the residual polarized νNH and νND band properties, measured for the isotopically diluted crystalline samples. Analysis of the band shapes of the four hydrogen isotope derivative crystals proved the existence of another kind of H/D isotopic effect, i.e. the long-range isotopic effect. It depends on an influence of the pyrazole ring hydrogen atoms onto the νNH and νND band widths and onto the band fine structures.

Effects of hydrogenated TiO2 nanotube arrays on protein adsorption and compatibility with osteoblast-like cells.

PubMed

Lu, Ran; Wang, Caiyun; Wang, Xin; Wang, Yuji; Wang, Na; Chou, Joshua; Li, Tao; Zhang, Zhenting; Ling, Yunhan; Chen, Su

2018-01-01

Modified titanium (Ti) substrates with titanium dioxide (TiO 2 ) nanotubes have broad usage as implant surface treatments and as drug delivery systems. To improve drug-loading capacity and accelerate bone integration with titanium, in this study, we hydrogenated anodized titanium dioxide nanotubes (TNTs) by a thermal treatment. Three groups were examined, namely: hydrogenated TNTs (H 2 -TNTs, test), unmodified TNTs (air-TNTs, control), and Ti substrates (Ti, control). Our results showed that oxygen vacancies were present in all the nanotubes. The quantity of -OH groups greatly increased after hydrogenation. Furthermore, the protein adsorption and loading capacity of the H 2 -TNTs were considerably enhanced as compared with the properties of the air-TNTs ( P <0.05). Additionally, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to investigate the interactions of TNTs with proteins. During the protein-loading process, the H 2 -TNTs not only enabled rapid protein adsorption, but also decreased the rate of protein elution compared with that of the air-TNTs. We found that the H 2 -TNTs exhibited better biocompatibility than the air-TNT and Ti groups. Both cell adhesion activity and alkaline phosphatase activity were significantly improved toward MG-63 human osteoblast-like cells as compared with the control groups ( P <0.05). We conclude that hydrogenated TNTs could greatly improve the loading capacity of bioactive molecules and MG-63 cell proliferation.

A new sniffer probe for the determination of hydrogen isotope ratios in the W7-AS stellarator

NASA Astrophysics Data System (ADS)

Zebisch, P.; Taglauer, E.

1999-07-01

An improved sniffer probe was constructed for measurements of the hydrogen isotope ratio and impurities in the plasma edge of the W7-AS stellarator. Details of the new design and the probe performance are presented. The new design allows changing the head without breaking the vacuum in the torus. It has a high mechanical stability, effective screening of the magnetic field and high sensitivity. The gas dynamic properties of the probe are analyzed using transmission line calculus, resulting in a rise time of 114 ms for hydrogen. During the 1997 spring measurement campaign, H/D isotope ratio measurements were carried through showing considerable outgassing of the walls during and after the discharge. He glow discharges reduce the isotope ratio drastically. Results from a typical experiment day are presented together with the analytic procedure for determining the isotope ratio in both the plasma edge and in the neutral gas region between the plasma and the vessel walls.

Large variations in the hydrology for the Paratethys-Mediterranean system during latest Miocene - insights from the hydrogen isotopes on biomarkers

NASA Astrophysics Data System (ADS)

Vasiliev, I.; Reichart, G. J.

2016-12-01

Paratethys - Mediterranean domain, occupying southern Eurasia and northern Africa, was a sea system characterized by recurrently restricted connections to the Open Ocean. To determine the nature of changes in the hydrological budget of the Paratethys - Mediterranean domain occurring during the latest Miocene we use compound-specific hydrogen isotope ratios on terrestrial and aquatic biomarkers extracted at four different locations: 1) the land based sedimentary succession located on Taman Peninsula in Russia, 2) the deep sea succession recovered in 1975 from the Black Sea, 3) the succession of Northern Apennines and Sicily from Italy and 4) the sedimentary infill of the Carpathians Foredeep from the Dacian Basin of Romania. The hydrogen isotopic compositions of n-alkanes (produced predominantly by higher plants) as well as alkenones (produced by haptophyte algae) indicate large environmental changes in the Paratethys-Mediterranean. The hydrogen isotopes of alkenones, showing an enrichment of more than 80‰ at the end of the Miocene, imply a major shift in basin hydrology, possibly resulting in severely increased salinity. These changes in hydrogen isotopic composition of the alkenones concur both with sharp shifts in reconstructed sea surface temperatures and mean annual temperatures. An interval with negative water budget was identified in all sections, most likely caused by enhanced evaporation during the Messinian salinity crisis (5.97 - 5.33 Ma). Additionally, the 60‰ amplitude of changes measured on long chain n-alkanes, produced predominantly by higher plants, can be principally explained by significant changes in the hydrogen isotopic composition of the precipitation reaching the Paratethys-Mediterranean system during the Messinian salinity crisis. These cumulated hydrogen isotopic compositions results indicate that the hydrological regime in Paratethys - Mediterranean domain has significantly varied, with heaviest δD values being recorded from a time

Influence of hydrogen bond accepting ability of anions on the adsorption performance of ionic liquid surface molecularly imprinted polymers.

PubMed

Zhu, Guifen; Gao, Xia; Wang, Xiaolong; Wang, Jianji; Fan, Jing

2018-01-12

To illuminate the influence mechanism of anionic structure of ionic liquids (ILs) on the adsorption performance of surface molecularly imprinted polymers (MIPs), in this work, six newly designed MIPs were prepared on the surface of amino-poly(styrene-divinylbenzene) particles by using imidazolium ILs with the same cation [C 4 mim] + but different anions (Cl, CH 3 SO 3 , PF 6 , BF 4 , C 4 F 7 O 2 , C 4 F 9 SO 3 ) as template molecules, methacrylic acid as functional monomer, and ethylene dimethacrylate as cross-linker. The resulting MIP materials were characterized by IR and SEM, and the influence of hydrogen bond accepting ability of anions on the adsorption performance of the MIPs for the ILs was investigated in acetonitrile. It was found that adsorption capacity of the MIPs towards the ILs decreased in the order MIP [C4mim][Cl]  > MIP [C4mim][C4F7O2]  ≥ MIP [C4mim][BF4] and MIP [C4mim][CH3SO3]  > MIP [C4mim][C4F9SO3]  > MIP [C4mim][PF6] , which is in good agreement with the ability of anions of the ILs to form hydrogen bonds. Ultraviolet, 1 H-NMR and 35 Cl-NMR spectroscopy was then used to study the interactions of anions of the ILs with the functional monomer. It was found that the hydrogen bond interaction between anions of the ILs and acidic proton of the functional monomer was the main driving force for the high adsorption selectivity of the imprinted polymers, and the stronger hydrogen bond interaction indicates higher binding capacity and higher selectivity of the polymers towards the ILs. It was also verified that the ILs with stronger hydrogen bond accepting ability of anions could be selectively extracted by the corresponding IL-MIPs. These results may provide new insight into the recognition mechanism of MIPs for ILs, and are also useful for the rational design of this new class of imprinting materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

NASA Astrophysics Data System (ADS)

Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

2016-12-01

Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

Project SQUID: The Viscosity of the Isotopes of Hydrogen and Their Intermolecular Force Potentials

DTIC Science & Technology

1963-12-01

values of the pseudo- Lennard - Jones potential for either hydrogen o- deuteriua. On the present evidence, and cn the present evidence alone, it would...W4drogesror deuterium forces the conclusion that neither gas obeys a lenrArd- Jones six- twelve potential , it is, nevertheless, useful to discuss the values...VISCOSITY OF THE ISOTOPES OF HYDROGEN AND THEIR INTERMOLECULAR FORCE POTENTIALS * by S. Kestir and A Nagashima Broow University December 1963 PROJECT SQUID

Alcohol molecules adsorption on graphane nanosheets - A first-principles investigation

NASA Astrophysics Data System (ADS)

Nagarajan, V.; Chandiramouli, R.

2018-05-01

The geometric structure, electronic and adsorption properties of methanol, ethanol and 1-propanol molecules on hydrogenated graphene (graphane) were investigated using first-principles calculations. The stability of graphane base material is confirmed using formation energy and phonon band structures. The adsorption of alcohol molecules on bare graphane and hydrogen vacant graphane nanosheet is found to be prominent and the selectivity of alcohol molecules can be achieved using bare or hydrogen vacant graphane nanosheet. Moreover, the interaction of alcohol molecules on bare and hydrogen vacant graphane nanosheets is studied using the adsorption energy, energy band gap variation, Bader charge transfer and average energy band gap variation. The adsorption energy ranges from -0.149 to -0.383 eV upon alcohol adsorption. The energy gap varies from 4.71 to 2.62 eV for bare graphane and from 4.02 to 3.60 eV for hydrogen vacant graphane nanosheets upon adsorption of alcohol molecules. The adsorption properties of alcohol molecules provide useful information for the possible application of graphane nanosheet as a base material for the detection of alcohol molecules.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michling, R.; Braun, A.; Cristescu, I.

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 themore » 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)« less

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)

Hydrogen and carbon isotopic composition of volatiles in Nakhla: Implications for weathering on Mars

NASA Technical Reports Server (NTRS)

Watson, L. L.; Epstein, S.; Stolper, E. M.

1992-01-01

Gases were collected at 120, 200, 300, 415, and 600 and 850 C. Hydrogen yields for the 600 and 850 C aliquots were measured separately and then the gases were combined for isotopic analysis. CO2 samples collected at the two lowest temperature steps amounted to less than 0.5 mu mole and were not analyzed isotopically. Excluding the 120 C temperature step, the bulk delta D of the sample was + 187 percent. Delta D values increase from -91 percent in the 120 C step to +518 percent in the 315 to 850 C step. The hydrogen content is greatest in the 120 C step and is roughly constant in the 200, 300, and 415 C aliquots. Between 415 C and 850 C, the yield drops off considerably. From 850 C to 950 C, virtually no H2 and only minor CO2 (less than 1 mu mole) were extracted. Using the isotopic analysis from the 300, 415, 600, and 850 C temperature collections, the bulk delta C-13 sub (PDB) is 0.0 percent. The heaviest component (delta C-13 sub (PDB) of +29 percent) was collected between 300 and 415 C. The release of hydrogen at the low temperatures reported here is consistent with the breakdown of the phases that constitute the alteration product between approx. 250 and 650 C. Although not as high as the present Martian atmosphere, the high delta D values are consistent with a Martian origin for the meteorites in question.

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

2015-07-02

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.

Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.

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

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

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 (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

NASA Astrophysics Data System (ADS)

Tang, Yongchun; Huang, Yongsong; Ellis, Geoffrey S.; Wang, Yi; Kralert, Paul G.; Gillaizeau, Bruno; Ma, Qisheng; Hwang, Rong

2005-09-01

A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C 13-C 21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ 13C values increase by ˜4‰ and δD values increase by ˜50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH ‡) and entropy (ΔΔS ‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C 20 ( n-icosane), the changes in enthalpy are calculated to be ˜1340 J mol -1 (320 cal mol -1) and 230 J mol -1 (55 cal mol -1) for D-H and 13C- 12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite

Intracrystalline site preference of hydrogen isotopes in borax

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » 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.« less

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

Comparison of two stable hydrogen isotope-ratio measurement techniques on Antarctic surface-water and ice samples

USGS Publications Warehouse

Hopple, J.A.; Hannon, J.E.; Coplen, T.B.

1998-01-01

A comparison of the new hydrogen isotope-ratio technique of Vaughn et al. ([Vaughn, B.H., White, J.W.C., Delmotte, M., Trolier, M., Cattani, O., Stievenard, M., 1998. An automated system for hydrogen isotope analysis of water. Chem. Geol. (Isot. Geosci. Sect.), 152, 309-319]; the article immediately preceding this article) for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the ??2H values determined by H2-H2O platinum equilibration, exhibiting a bias of +0.5??? and a 2 - ?? variation of 1.9???. The isotopic results of 10 reduction technique samples, however, gave ??2H values that differed by 3.5??? or more, and were too negative by as much as 5.4??? and too positive by as much as 4.9??? with respect to those determined using the platinum equilibration technique.

[Impacts of dominated landscape types on hydrogen and oxygen isotope effects of spring water in the Hani Rice Terraces].

PubMed

Jiao, Yuan Mei; Liu, Cheng Jing; Liu, Xin; Liu, Zhi Lin; Ding, Yin Ping

2017-07-18

Analysis of hydrogen and oxygen stable isotopes is an effective method to track the water cycle in watershed. Impact of landscape pattern on the isotope effects of spring water is a new interdisciplinary topic between landscape ecology and isotope hydrology. Taking the Quanfuzhuang River basin located in the core area of UNESCO World Cultural Heritage of Honghe Hani Rice Terrace as the object, collecting the monthly samples of 78 points of spring water and 39 precipitation at altitude of 1500 m (terraces), 1700 m (terraces) and 1900 m (forest) from March 2015 to March 2016, we analyzed the hydrogen and oxygen stable isotopes of water samples under the different landscape types. The results indicated that the dominated landscape types were forests and rice terraces, being 66.6% and 22.1% of the whole landscape area respectively, and they had a spatial vertical pattern of forest located at the mountain top and rice terraces at the down-slope. The correlation analysis showed that the spring water not only came from the precipitation, but also from other water sources which had a more positive δ 18 O and δD values, the spring water in up-slope forests mainly came from precipitation, while that in down-slope rice terraces came from precipitation, ri-ver water, rice terrace water and under ground water. Therefore, the mixing effects of spring water δ 18 O and δD were more significant in rice terraces. The overall altitude effect of the hydrogen and oxygen stable isotopes in spring water was obvious. The linear decreasing rates of δ 18 O and δD values were -0.125‰·(100 m) -1 and -0.688‰·(100 m) -1 , respectively. The deuterium surplus value increased with the altitude because of the impacts of landscape pattern and the local cycle of water isotopes. In summary, the dominant landscape types had a significant impact on the hydrogen and oxygen isotopes of spring water, which could be used as response indicator to reveal the impacts of landscape pattern on

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

PubMed

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

2010-02-24

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

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.

Determination of stable carbon and hydrogen isotopes of light hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dumke, I.; Faber, E.; Poggenburg, J.

1989-10-01

A combined system for the measurement of {sup 13}C/{sup 12}C and D/H ratios on light hydrocarbons (C{sub 1}-C{sub 3}) and CO{sub 2} is described. The system is designed for natural gas and sediment gas analyses. It comprises gas chromatographic separation with online combustion of hydrocarbons to CO{sub 2} and H{sub 2}O, reduction of H{sub 2}O to H{sub 2} on zinc in closed ampules, and mass spectrometric determination of isotope ratios ({delta}{sup 13}C, {delta}D) using a mass spectrometer inlet system especially designed for low hydrogen gas quantities. Isotope analyses can be carried out in the range of 3-10,000 {mu}L of CO{submore » 2} and 100-10,000 {mu}L of H{sub 2} (gas quantities converted from sample compounds during preparation, STP). Including all preparation steps, reproducibility of isotope values for large sample quantities (>100 {mu}L of produced CO{sub 2} and >1,000 {mu}L of produced H{sub 2}). is {plus minus}0.2{per thousand} for {delta}{sup 13}C and {plus minus}3{per thousand} for {delta}D.« less

Hydrogen Chemical Configuration and Thermal Stability in Tungsten Disulfide Nanoparticles Exposed to Hydrogen Plasma

PubMed Central

Laikhtman, Alex; Makrinich, Gennady; Sezen, Meltem; Yildizhan, Melike Mercan; Martinez, Jose I.; Dinescu, Doru; Prodana, Mariana; Enachescu, Marius; Alonso, Julio A.; Zak, Alla

2017-01-01

The chemical configuration and interaction mechanism of hydrogen adsorbed in inorganic nanoparticles of WS2 are investigated. Our recent approaches of using hydrogen activated by either microwave or radiofrequency plasma dramatically increased the efficiency of its adsorption on the nanoparticles surface. In the current work we make an emphasis on elucidation of the chemical configuration of the adsorbed hydrogen. This configuration is of primary importance as it affects its adsorption stability and possibility of release. To get insight on the chemical configuration, we combined the experimental analysis methods with theoretical modeling based on the density functional theory (DFT). Micro-Raman spectroscopy was used as a primary tool to elucidate chemical bonding of hydrogen and to distinguish between chemi- and physisorption. Hydrogen adsorbed in molecular form (H2) was clearly identified in all the plasma-hydrogenated WS2 nanoparticles samples. It was shown that the adsorbed hydrogen is generally stable under high vacuum conditions at room temperature, which implies its stability at the ambient atmosphere. A DFT model was developed to simulate the adsorption of hydrogen in the WS2 nanoparticles. This model considers various adsorption sites and identifies the preferential locations of the adsorbed hydrogen in several WS2 structures, demonstrating good concordance between theory and experiment and providing tools for optimizing of hydrogen exposure conditions and the type of substrate materials. PMID:28596812

Late Holocene dinosterol hydrogen isotope variability in Lac Lalolalo and Lac Lanutavake on Wallis Island

NASA Astrophysics Data System (ADS)

Maloney, A. E.; Hing, S. N.; Richey, J. N.; Nelson, D. B.; Sachs, J. P.

2017-12-01

The South Pacific Convergence Zone (SPCZ) is the Southern Hemisphere's largest precipitation feature, yet little is known about the region's rainfall prior to the instrumental record. In the tropics, hydrogen isotopes of precipitation are controlled by the "amount effect" where higher mean annual rainfall rates result in 2H-depleted rain. In turn, hydrogen isotopes in tropical lakes are influenced by both rain water isotopes and evaporative enrichment. Molecular fossils preserved in lake sediments offer a promising tool for improving our understanding of the past SPCZ by tracking changes in lake water isotopes. Hydrogen isotope compositions (δ2H) of the algal lipid biomarker dinosterol were measured in duplicate sediment cores from lakes 2.75km apart on Wallis Island. The modern lakes differ in physical and chemical conditions but are both freshwater in the photic zone and experience identical climate conditions. They are an ideal setting to investigate the fidelity to which δ2Hdinosterol records climate. Duplicate records from Lac Lanutavake are in excellent agreement and reveal little change in during the past 1700 years with minor δ2Hdinosterol fluctuations between -280‰ and -290‰. Duplicate records from Lac Lalolalo also agree extremely well during the past 2,000 years. However, contrary to its neighbor, Lac Lalolalo has a highly variable δ2Hdinosterol history with 2H-depleted values of -300‰ during the youngest part of the record climbing to 2H-enriched values of -230‰ around 1000-2000 years ago. The large shift in Lac Lalolalo δ2Hdinosterol may be due to changes in lake biogeochemistry that impact growth conditions or shifts in dinoflagellate species composition. Alternatively, if the Lac Lalolalo record actually reflects changes in hydrology, large limnological changes must have occurred in Lac Lanutavke to mute the climate signal. This work emphasizes the importance of redundancy and duplication when investigating changes in past climate using

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oerter, Erik; Singleton, Michael; Davisson, Lee

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE PAGES

Oerter, Erik; Singleton, Michael; Davisson, Lee

2017-10-22

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stable hydrogen isotope analysis as a method to identify illegally trapped songbirds.

PubMed

Kelly, Andrew; Thompson, Richard; Newton, Jason

2008-06-01

We measured stable hydrogen isotope ratios in the primary feathers of two subspecies of goldfinches, confiscated by the Police and the Royal Society for the Prevention of Cruelty to Animals (RSPCA) on suspicion that they had been illegally taken from the wild. We found significant differences in the delta2H values of the two subspecies indicating that they were sourced from different geographical regions. Our results correlated with isotopic precipitation maps and with the known distribution of the two subspecies of goldfinch. We believe that this technique could be used by law enforcement agencies to determine the origin of birds in cases where the species or subspecies involved are geographically distinct.

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.

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

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

DOE PAGES

Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

2013-06-03

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity inmore » recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.« less

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).

PubMed

Matthes, Jochen; Pery, Tal; Gründemann, Stephan; Buntkowsky, Gerd; Sabo-Etienne, Sylviane; Chaudret, Bruno; Limbach, Hans-Heinrich

2004-07-14

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.

What Drives Hydrogen Isotopic Variability Recorded by Biomarkers in Sediments of Lake Karakul, Pamir?

NASA Astrophysics Data System (ADS)

Aichner, B.; Mischke, S.; Pausata, F. S. R.; Werner, M.; Zhang, Q.; Heinecke, L.; Feakins, S. J.; Sachse, D.; Mahmoudov, Z.; Rajabov, I.

2017-12-01

Central Asia is a climate sensitive region located at the boundary of large scale atmospheric circulation systems. To examine glacial to interglacial hydrological changes in the region, we analysed the hydrogen isotopic composition (δD values) of n-alkanes in a 30-ka record from Lake Karakul, eastern Pamir (altitude: 3,915m, MAT: -3.9 °C, MAP: 82 mm). δD values of both aquatic and terrestrial compounds showed distinct trends throughout the studied time interval, with generally higher values during the glacial and lower values during the Holocene, and variability of up to 60‰. In particular shifts towards higher δD values were observed for aquatic biomarkers at ca. 30, 27, and 15 ka BP. Temperature and precipitation effects alone cannot explain the higher δD values during the glacial and the large isotopic amplitudes. To explain these observations we conducted a set of experiments using atmospheric models with embedded isotope modules (CAM3iso- and ECHAM5-wiso). We assume that terrestrial n-alkanes mainly record the isotopic signature of summer precipitation within the lower elevated parts of the Karakul Basin. Based on the model output we hypothesize that shifts between local and more distant vapour sources are the reason behind the trends within isotopic data. Data derived from aquatic biomarkers are more difficult to explain due to multiple influencing factors on δD of the lake water. Assuming that the lake water integrates an annual isotopic signal from the whole lake catchment, we suggest that a change in precipitation seasonality drives the large variability of hydrogen isotopic values. This is in agreement with the models, which suggest reduced winter (more negative δD) and slightly higher summer precipitation (more positive δD) during the glacial compared to the Holocene. Consequently, a net-increase of isotopically enriched inflow into the lake could explain the three distinct shifts towards higher δD values. Expansion of terrestrial vegetation

Hydrogen Isotope Fractionation during the Biodegradation of 1,2-Dichloroethane: Potential for Pathway Identification Using a Multi-element (C, Cl, and H) Isotope Approach.

PubMed

Palau, Jordi; Shouakar-Stash, Orfan; Hatijah Mortan, Siti; Yu, Rong; Rosell, Monica; Marco-Urrea, Ernest; Freedman, David L; Aravena, Ramon; Soler, Albert; Hunkeler, Daniel

2017-09-19

Even though multi-element isotope fractionation patterns provide crucial information with which to identify contaminant degradation pathways in the field, those involving hydrogen are still lacking for many halogenated groundwater contaminants and degradation pathways. This study investigates for the first time hydrogen isotope fractionation during both aerobic and anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) using five microbial cultures. Transformation-associated isotope fractionation values (ε bulk H ) were -115 ± 18‰ (aerobic C-H bond oxidation), -34 ± 4‰ and -38 ± 4‰ (aerobic C-Cl bond cleavage via hydrolytic dehalogenation), and -57 ± 3‰ and -77 ± 9‰ (anaerobic C-Cl bond cleavage via reductive dihaloelimination). The dual-element C-H isotope approach (Λ C-H = Δδ 2 H/Δδ 13 C ≈ ε bulk H /ε bulk C , where Δδ 2 H and Δδ 13 C are changes in isotope ratios during degradation) resulted in clearly different Λ C-H values: 28 ± 4 (oxidation), 0.7 ± 0.1 and 0.9 ± 0.1 (hydrolytic dehalogenation), and 1.76 ± 0.05 and 3.5 ± 0.1 (dihaloelimination). This result highlights the potential of this approach to identify 1,2-DCA degradation pathways in the field. In addition, distinct trends were also observed in a multi- (i.e., Δδ 2 H versus Δδ 37 Cl versus Δδ 13 C) isotope plot, which opens further possibilities for pathway identification in future field studies. This is crucial information to understand the mechanisms controlling natural attenuation of 1,2-DCA and to design appropriate strategies to enhance biodegradation.

Adsorption and desorption of hydrogen at nonpolar GaN (1 1 ¯ 00 ) surfaces: Kinetics and impact on surface vibrational and electronic properties

NASA Astrophysics Data System (ADS)

Lymperakis, L.; Neugebauer, J.; Himmerlich, M.; Krischok, S.; Rink, M.; Kröger, J.; Polyakov, V. M.

2017-05-01

The adsorption of hydrogen at nonpolar GaN (1 1 ¯00 ) surfaces and its impact on the electronic and vibrational properties is investigated using surface electron spectroscopy in combination with density functional theory (DFT) calculations. For the surface mediated dissociation of H2 and the subsequent adsorption of H, an energy barrier of 0.55 eV has to be overcome. The calculated kinetic surface phase diagram indicates that the reaction is kinetically hindered at low pressures and low temperatures. At higher temperatures ab initio thermodynamics show, that the H-free surface is energetically favored. To validate these theoretical predictions experiments at room temperature and under ultrahigh vacuum conditions were performed. They reveal that molecular hydrogen does not dissociatively adsorb at the GaN (1 1 ¯00 ) surface. Only activated atomic hydrogen atoms attach to the surface. At temperatures above 820 K, the attached hydrogen gets desorbed. The adsorbed hydrogen atoms saturate the dangling bonds of the gallium and nitrogen surface atoms and result in an inversion of the Ga-N surface dimer buckling. The signatures of the Ga-H and N-H vibrational modes on the H-covered surface have experimentally been identified and are in good agreement with the DFT calculations of the surface phonon modes. Both theory and experiment show that H adsorption results in a removal of occupied and unoccupied intragap electron states of the clean GaN (1 1 ¯00 ) surface and a reduction of the surface upward band bending by 0.4 eV. The latter mechanism largely reduces surface electron depletion.

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.

Hydrogen isotope fractionation between C-H-O species in magmatic fluids

NASA Astrophysics Data System (ADS)

Foustoukos, D. I.; Mysen, B. O.

2012-12-01

Constraining the hydrogen isotope fractionation between H-bearing volatiles (e.g. H2, CH4, hydrocarbons, H2O) as function of temperature and pressure helps to promote our understanding of the isotopic composition of evolved magmatic fluids and the overall mantle-cycling of water and reduced C-O-H volatiles. To describe the thermodynamics of the exchange reactions between the different H/D isotopologues of H2 and CH4 under supercritical water conditions, a novel experimental technique has been developed by combining vibrational Raman spectroscopy with hydrothermal diamond anvil cell designs (HDAC), which offers a method to monitor the in-situ evolution of H/D containing species. To this end, the equilibrium relationship between H2-D2-HD in supercritical fluid was investigated at temperatures ranging from 300 - 800 oC and pressures ~ 0.3 - 1.3 GPa [1]. Experimental results obtained in-situ and ex-situ show a significant deviation from the theoretical values of the equilibrium constant predicted for ideal-gas reference state, and with an apparent negative temperature effect triggered by the enthalpy contributions due to mixing in supercritical water. Here, we present a series of HDAC experiments conducted to evaluate the role of supercritical water on the isotopic equilibrium between H/D methane isotopologues at 600 - 800 oC and 409 - 1622 MPa. In detail, tetrakis-silane (Si5C12H36) was reacted with H2O-D2O aqueous solution in the presence of either Ni or Pt metal catalyst, resulting to the formation of deuterated methane species such as CH3D, CHD3, CH2D2 and CD4. Two distinctly different set of experiments ("gas phase"; "liquid phase") were performed by adjusting the silane/water proportions. By measuring the relative intensities of Raman vibrational modes of species, experimental results demonstrate distinctly different thermodynamic properties for the CH4-CH3D-CHD3-CH2D2 equilibrium in gas and liquid-water-bearing systems. In addition, the D/H molar ratio of

Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo

2017-03-01

A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification.

Evaluating the role of re-adsorption of dissolved Hg 2+ during cinnabar dissolution using isotope tracer technique

DOE PAGES

Jiang, Ping; Li, Yanbin; Liu, Guangliang; ...

2016-06-02

Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbedmore » Hg on cinnabar surface via the reduction in spiked 202Hg 2+. By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred g L –1, while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. Lastly, these results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies.« less

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

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.

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

PubMed

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

2017-03-30

Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and

Highly effective hydrogen isotope separation in nanoporous metal-organic frameworks with open metal sites: direct measurement and theoretical analysis.

PubMed

Oh, Hyunchul; Savchenko, Ievgeniia; Mavrandonakis, Andreas; Heine, Thomas; Hirscher, Michael

2014-01-28

Separating gaseous mixtures that consist of very similar size is one of the critical issues in modern separation technology. Especially, the separation of the isotopes hydrogen and deuterium requires special efforts, even though these isotopes show a very large mass ratio. Conventionally, H/D separation can be realized through cryogenic distillation of the molecular species or the Girdler-sulfide process, which are among the most energy-intensive separation techniques in the chemical industry. However, costs can be significantly reduced by using highly mass-selective nanoporous sorbents. Here, we describe a hydrogen isotope separation strategy exploiting the strongly attractive open metal sites present in nanoporous metal-organic frameworks of the CPO-27 family (also referred to as MOF-74). A theoretical analysis predicts an outstanding hydrogen isotopologue separation at open metal sites due to isotopal effects, which has been directly observed through cryogenic thermal desorption spectroscopy. For H2/D2 separation of an equimolar mixture at 60 K, the selectivity of 12 is the highest value ever measured, and this methodology shows extremely high separation efficiencies even above 77 K. Our theoretical results imply also a high selectivity for HD/H2 separation at similar temperatures, and together with catalytically active sites, we propose a mechanism to produce D2 from HD/H2 mixtures with natural or enriched deuterium content.

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

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.

Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope.

PubMed

Hamuro, Yoshitomo

2017-03-01

A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification. Graphical Abstract ᅟ.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zamfirache, M.; Bornea, A.; Stefanescu, I.

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 hydrogenmore » 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)« less

Isotope composition of secondary hydrogen and helium above the atmosphere measured by the instruments NINA and NINA-2

NASA Astrophysics Data System (ADS)

Bidoli, V.; Casolino, M.; de Pascale, M.; Furano, G.; Iannucci, A.; Morselli, A.; Picozza, P.; Sparvoli, R.; Bakaldin, A.; Galper, A.; Koldashov, S.; Korotkov, M.; Leonov, A.; Mikhailov, V.; Voronov, S.; Boezio, M.; Bonvicini, V.; Vacchi, A.; Zampa, G.; Zampa, N.; Ambriola, M.; Cafagna, F.; Circella, M.; de Marzo, C.; Adriani, O.; Papini, P.; Spillantini, P.; Straulino, S.; Vannuccini, E.; Ricci, M.; Castellini, G.

2003-05-01

In this paper we report on the energy spectra and abundance ratios of hydrogen and helium isotopes of albedo origin, measured by the instruments NINA and NINA-2 in near-equatorial regions. The instrument NINA flew on board the satellite Resurs-01-N4 between 1998 and 1999, at a 830 km average altitude. The NINA-2 apparatus, on board the satellite MITA, was put into orbit in July 2000 at an altitude of about 450 km. NINA and NINA-2 measurements revealed that 2H, 3H, 3He, and 4He are a significant portion of the secondary flux above the atmosphere. The energy spectra of hydrogen isotopes are practically flat across the energy range of 10-40 MeV/n, while the spectra of helium isotopes can be fitted by a power law of spectral indexes γ = 0.8 and γ = 1.5 for 3He and 4He, respectively.

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

Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage.

PubMed

Jin, Jiao; Ouyang, Jing; Yang, Huaming

2017-12-01

Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage

NASA Astrophysics Data System (ADS)

Jin, Jiao; Ouyang, Jing; Yang, Huaming

2017-03-01

Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.

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

Evaluating the role of re-adsorption of dissolved Hg(2+) during cinnabar dissolution using isotope tracer technique.

PubMed

Jiang, Ping; Li, Yanbin; Liu, Guangliang; Yang, Guidi; Lagos, Leonel; Yin, Yongguang; Gu, Baohua; Jiang, Guibin; Cai, Yong

2016-11-05

Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbed Hg on cinnabar surface via the reduction in spiked (202)Hg(2+). By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred μgL(-1), while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. These results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Systematics of isotopic production cross sections from interactions of relativistic 40Ca in hydrogen

NASA Astrophysics Data System (ADS)

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

1997-09-01

The isotopic production cross sections for 40Ca projectiles at 357, 565, and 763 MeV/nucleon interacting in a liquid hydrogen target have been measured by the Transport Collaboration at the LBL HISS facility. The systematics of these cross sections are studied, and the results indicate that nuclear structure effects are present in the isotope production process during the relativistic collisions. The newly measured cross sections are also compared with those predicted by semiempirical and parametric formulas, but the predictions do not fully describe the systematics such as the energy dependence. The consequences of the cross section systematics in galactic cosmic ray studies are also discussed.

The Evolution of Water in Martian Atmosphere, Hydrosphere, and Cryosphere: Insights from Hydrogen Isotopes

NASA Astrophysics Data System (ADS)

Usui, T.; Kurokawa, H.; Alexander, C.; Simon, J. I.; Wang, J.; Jones, J. H.

2016-12-01

Mars exploration missions provide compelling evidence for the presence of liquid water during the earliest geologic era (Noachian: > 3.9 Ga) of Mars. The amount and stability of liquid water on the surface is strongly influenced by the composition and pressure of the atmosphere. However, the evolution of Noachian atmosphere has been poorly constrained due to uncertainties of atmospheric loss regimes and internal/external factors such as impact flux and volcanic degassing. We can trace the evolution of the early Martian atmosphere and its interaction with the hydrosphere and cryosphere with hydrogen isotope ratios (D/H) because they fractionate during atmospheric escape and during hydrological cycling between the atmosphere, surface waters, and the polar ice caps. This study reports D/H ratios of primordial and 4 Ga-old atmosphere by ion microprobe analyses of Martian meteorites. Analyses of olivine-hosted glass inclusions in the most primitive shergottite (Yamato 980459) provide a near-chondritic D/H ratio (1.3×SMOW) for the 4.5 Ga primordial water preserved in the mantle. On the other hand, carbonates in Allan Hills 84001 provide a D/H range (1.5-2.0×SMOW) for the Noachian surface water that was isotopically equilibrated with the 4 Ga atmosphere. The latter observation requires that even after the Noachian period the hydrogen isotopes were fractionated significantly to reach the present-day value of 6×SMOW. Using the one-reservoir model of Kurokawa et al. (2014) we can provide minimum estimates on the amounts of hydrogen loss before and after 4 Ga based on the D/H data from the meteorites (1.3×SMOW at 4.5 Ga and 1.5-2.0×SMOW at 4 Ga) assuming the volume of polar surface-ice (20-30 m global equivalent layers, GEL). The model indicates that the hydrogen loss during the first 0.5 billion years (16-54 m GEL) was comparable to those (42-93 mGEL) in the remaining Martian history. These values are distinctly lower than the geological estimates on the volumes of

Towards a palaeosalinity proxy: hydrogen isotopic fractionation between source water and lipids produced via different biosynthetic pathways in haptophyte algae

NASA Astrophysics Data System (ADS)

Chivall, David; M'Boule, Daniela; Heinzelmann, Sandra M.; Kasper, Sebastian; Sinke-Schoen, Daniëlle; Sininnghe-Damsté, Jaap S.; Schouten, Stefan; van der Meer, Marcel T. J.

2014-05-01

Palaeosalinity is one of the most important oceanographic parameters that cannot currently be quantified with reasonable accuracy from sedimentary records. Hydrogen isotopic fractionation between water and alkenones is dependent, amongst other factors, upon the salinity in which alkenone-producing haptophyte algae grow and is represented by the fractionation factor, α, increasing with salinity.1 As such, the hydrogen isotopic composition of alkenones is emerging as a palaeosalinity proxy. Understanding the mechanism behind the sensitivity of fractionation to salinity is important for the correct application of the proxy, however this mechanism is currently unknown. Here we present hydrogen isotopic compositions of lipids produced via different biosynthetic pathways from batch cultures of Emiliania huxleyi CCMP 1516 and Isochrysis galbana CCMP 1323 grown over a range of salinities and discuss the possible sources of the sensitivity of hydrogen isotope fractionation to salinity. α for C37 alkenones (produced via an unknown biosynthetic pathway but assumed to be acetogenic; e.g.2) and that for C14:0, C16:0, and C18:1 fatty acids (acetogenic) from exponential growth phase I. galbana show a similar sensitivity to salinity, increasing at 0.0013-0.0019 per salinity unit (S-1). Meanwhile, in exponential growth phase E. huxleyi, α for C37 alkenones and α for brassicasterol (mevalonate pathway) increase at 0.0015-0.0022 S-1, but α for phytol (methylerythritol pathway) shows no significant relationship with salinity. These results suggest that fractionation is sensitive to salinity for lipids formed both in the chloroplast and cytosol. They also suggest that the sensitivity may either originate in glyceralde-3-phosphate or pyruvate but is then lost through hydrogen exchange with cell water during sugar rearrangements in the methylerythritol pathway or sensitivity originates with the production and consumption of acetate. References Schouten, S., Ossebaar, J., Schreiber

Vanadium isotopic composition of the sea squirt (Ciona savignyi).

PubMed

Nomura, Masao; Nakamura, Mana; Soeda, Ryosuke; Kikawada, Yoshikazu; Fukushima, Michiko; Oi, Takao

2012-09-01

Vanadium (V) in the sea squirt (Ciona savignyi) from Onagawa Bay, Miyagi, Japan, was isolated and purified through adsorption on a diamine resin and anion and cation exchanges after the dissolution of sea squirt samples with nitric acid and hydrogen peroxide. The (50)V/(51)V isotope ratio of V thus obtained was mass-spectrometrically determined to be from 2.51×10(-3) to 2.55×10(-3) with the average of 2.53×10(-3) by the thermal ionisation technique. This value agreed with those of vanadyl chloride and vanadyl nitrate both prepared from vanadyl sulphate (Wako Pure Chemical Industries, Ltd., Japan) and of V in coastal seawater (Shimokita Peninsula, Aomori, Japan) within experimental uncertainties (standard deviation of±0.04), which suggested that no appreciable V isotope fractionation occurs accompanying V uptake by the sea squirt from sea water.

Isotope effects associated with tunneling and double proton transfer in the hydrogen bonds of benzoic acid

NASA Astrophysics Data System (ADS)

Xue, Q.; Horsewill, A. J.; Johnson, M. R.; Trommsdorff, H. P.

2004-06-01

The isotope effects associated with double proton transfer in the hydrogen bonds of benzoic acid (BA) dimers have been measured using field-cycling 1H NMR relaxometry and quasielastic neutron scattering. By studying mixed isotope (hydrogen and deuterium) samples, the dynamics of three isotopologues, BA-HH, BA-HD, and BA-DD, have been investigated. Low temperature measurements provide accurate measurements of the incoherent tunneling rate, k0. This parameter scales accurately with the mass number, m, according to the formula k0=(E/m)e-F√m providing conclusive evidence that the proton transfer process is a strongly correlated motion of two hydrons. Furthermore, we conclude that the tunneling pathway is the same for the three isotopologue species. Measurements at higher temperatures illuminate the through barrier processes that are mediated via intermediate or excited vibrational states. In parallel with the investigation of proton transfer dynamics, the theoretical and experimental aspects of studying spin-lattice relaxation in single crystals of mixed isotope samples are investigated in depth. Heteronuclear dipolar interactions between 1H and 2H isotopes contribute significantly to the overall proton spin-lattice relaxation and it is shown that these must be modeled correctly to obtain accurate values for the proton transfer rates. Since the sample used in the NMR measurements was a single crystal, full account of the orientation dependence of the spin-lattice relaxation with respect to the applied B field was incorporated into the data analysis.

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.

The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

NASA Astrophysics Data System (ADS)

Horita, Juske; Cole, David R.; Wesolowski, David J.

1995-03-01

The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

Adsorption de gaz sur les materiaux microporeux modelisation, thermodynamique et applications

NASA Astrophysics Data System (ADS)

Richard, Marc-Andre

2009-12-01

Nos travaux sur l'adsorption de gaz dans les materiaux microporeux s'inscrivent dans le cadre des recherches visant a augmenter l'efficacite du stockage de l'hydrogene a bord des vehicules. Notre objectif etait d'etudier la possibilite d'utiliser l'adsorption afin d'ameliorer l'efficacite de la liquefaction de l'hydrogene des systemes a petite echelle. Nous avons egalement evalue les performances d'un systeme de stockage cryogenique de l'hydrogene base sur la physisorption. Comme nous avons affaire a des plages de temperatures particulierement etendues et a de hautes pressions dans la region supercritique du gaz, nous avons du commencer par travailler sur la modelisation et la thermodynamique de l'adsorption. La representation de la quantite de gaz adsorbee en fonction de la temperature et de la pression par un modele semi-empirique est un outil utile pour determiner la masse de gaz adsorbee dans un systeme mais egalement pour calculer les effets thermiques lies a l'adsorption. Nous avons adapte le modele Dubinin-Astakhov (D-A) pour modeliser des isothermes d'adsorption d'hydrogene, d'azote et de methane sur du charbon actif a haute pression et sur une grande plage de temperatures supercritiques en considerant un volume d'adsorption invariant. Avec cinq parametres de regression (incluant le volume d'adsorption Va), le modele que nous avons developpe permet de tres bien representer des isothermes experimentales d'adsorption d'hydrogene (de 30 a 293 K, jusqu'a 6 MPa), d'azote (de 93 a 298 K, jusqu'a 6 MPa) et de methane (de 243 a 333 K, jusqu'a 9 MPa) sur le charbon actif. Nous avons calcule l'energie interne de la phase adsorbee a partir du modele en nous servant de la thermodynamique des solutions sans negliger le volume d'adsorption. Par la suite, nous avons presente les equations de conservation de la niasse et de l'energie pour un systeme d'adsorption et valide notre demarche en comparant des simulations et des tests d'adsorption et de desorption. En plus de l

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates.

PubMed

Mitchell, Martha C; Gallo, Marco; Nenoff, Tina M

2004-07-22

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates

NASA Astrophysics Data System (ADS)

Mitchell, Martha C.; Gallo, Marco; Nenoff, Tina M.

2004-07-01

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

First Principles Study of Adsorption of Hydrogen on Typical Alloying Elements and Inclusions in Molten 2219 Al Alloy.

PubMed

Liu, Yu; Huang, Yuanchun; Xiao, Zhengbing; Jia, Guangze

2017-07-19

To better understand the effect of the components of molten 2219 Al alloy on the hydrogen content dissolved in it, the H adsorption on various positions of alloying element clusters of Cu, Mn and Al, as well as the inclusion of Al₂O₃, MgO and Al₄C₃, were investigated by means of first principles calculation, and the thermodynamic stability of H adsorbed on each possible site was also studied on the basis of formation energy. Results show that the interaction between Al, MgO, Al₄C₃ and H atoms is mainly repulsive and energetically unfavorable; a favorable interaction between Cu, Mn, Al₂O₃ and H atoms was determined, with H being more likely to be adsorbed on the top of the third atomic layer of Cu(111), the second atomic layer of Mn(111), and the O atom in the third atomic layer of Al₂O₃, compared with other sites. It was found that alloying elements Cu and Mn and including Al₂O₃ may increase the hydrogen adsorption in the molten 2219 Al alloy with Al₂O₃ being the most sensitive component in this regard.

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

PubMed

Baune, Claudia; Bottcher, Michael E

2010-12-01

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

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

USGS Publications Warehouse

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

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.

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.

Structural changes caused by H 2 adsorption on the Si(111)7 × 7 surface

NASA Astrophysics Data System (ADS)

Wolff, S. H.; Wagner, S.; Gibson, J. M.; Loretto, D.; Robinson, I. K.; Bean, J. C.

1990-12-01

Structural changes caused by the adsorption of molecular hydrogen adsorption onto the Si(111)7 × 7 surface reconstruction are quantified using the first structure parameter refinement on transmission electron diffraction (TED) data. We find that initial adsorption of molecular hydrogen onto the Si(111)7 × 7 surface causes a preferential decrease in the occupancy of the center adatoms. Further adsorption of hydrogen results in the breaking of the dimer bonds and the removal of the corner adatoms.

Hydrogen stable isotopic constraints on methane emissions from oil and gas extraction in the Colorado Front Range, USA

NASA Astrophysics Data System (ADS)

Townsend-Small, A.; Botner, E. C.; Jimenez, K.; Blake, N. J.; Schroeder, J.; Meinardi, S.; Barletta, B.; Simpson, I. J.; Blake, D. R.; Flocke, F. M.; Pfister, G.; Bon, D.; Crawford, J. H.

2015-12-01

The climatic implications of a shift from oil and coal to natural gas depend on the magnitude of fugitive emissions of methane from the natural gas supply chain. Attempts to constrain methane emissions from natural gas production regions can be confounded by other sources of methane. Here we demonstrate the utility of stable isotopes, particularly hydrogen isotopes, for source apportionment of methane emissions. The Denver, Colorado area is home to a large oil and gas field with both conventional oil and gas wells and newer hydraulic fracturing wells. The region also has a large metropolitan area with several landfills and a sizable cattle population. As part of the DISCOVER-AQ and FRAPPE field campaigns in summer 2014, we collected three types of canister samples for analysis of stable isotopic composition of methane: 1), samples from methane sources; 2), samples from two stationary ground sites, one in the Denver foothills, and one in an oil and gas field; and 3), from the NCAR C-130 aircraft in samples upwind and downwind of the region. Our results indicate that hydrogen isotope ratios are excellent tracers of sources of methane in the region, as we have shown previously in California and Texas. Use of carbon isotope ratios is complicated by the similarity of natural gas isotope ratios to that of background methane. Our results indicate that, despite the large amount of natural gas production in the region, biological sources such as cattle feedlots and landfills account for at least 50% of total methane emissions in the Front Range. Future work includes comparison of isotopes and alkane ratios as tracers of methane sources, and calculation of total methane fluxes in the region using continuous measurements of methane concentrations during aircraft flights.

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.

Difference in the stable isotopic fractionations of Ce, Nd, and Sm during adsorption on iron and manganese oxides and its interpretation based on their local structures

NASA Astrophysics Data System (ADS)

Nakada, Ryoichi; Tanimizu, Masaharu; Takahashi, Yoshio

2013-11-01

Many elements have become targets for studies of stable isotopic fractionation with the development of various analytical techniques. Although several chemical factors that control the isotopic fractionation of heavy elements have been proposed, it remains controversial which properties are most important for the isotopic fractionation of elements. In this study, the stable isotopic fractionation of neodymium (Nd) and samarium (Sm) during adsorption on ferrihydrite and δ-MnO2 was examined. This examination was combined with speciation analyses of these ions adsorbed on the solid phases by extended X-ray absorption fine structure (EXAFS) spectroscopy. Neodymium isotope ratios for Nd on ferrihydrite and δ-MnO2 systems were, on average, 0.166‰ and 0.410‰ heavier than those of the liquid phase, which correspond to mean isotopic fractionation factors between the liquid and solid phases (αLq-So) of Nd on ferrihydrite and δ-MnO2 of 0.999834 (2σ = ±0.000048) and 0.999590 (2σ = ±0.000106), respectively. Similarly, averaged Sm isotope ratios on ferrihydrite and δ-MnO2 were 0.206‰ and 0.424‰ heavier than those of the liquid phase and the corresponding αLq-So values were 0.999794 (±0.000041) and 0.999576 (±0.000134), respectively. These results indicate that the directions of isotopic fractionation in the Nd and Sm systems are in contrast with that recently found for Ce(III) systems despite the similar chemical characteristics of rare earth elements. EXAFS analyses suggest that the bond length of the first coordination sphere (REE-O bond) of Nd and Sm adsorbed on δ-MnO2 is shorter than that of their aqua ions, although this was not clear for the ferrihydrite systems. The shorter bond length relative to the aqua ion is indicative of a stronger bond, suggesting that the equilibrium isotopic fractionation for the Nd and Sm systems can be governed by bond strength as has often been discussed for isotopic fractionation in solid-water adsorption systems

Isotope composition and volume of Earth's early oceans.

PubMed

Pope, Emily C; Bird, Dennis K; Rosing, Minik T

2012-03-20

Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

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

Production of carbon monoxide-free hydrogen and helium from a high-purity source

DOEpatents

Golden, Timothy Christopher [Allentown, PA; Farris, Thomas Stephen [Bethlehem, PA

2008-11-18

The invention provides vacuum swing adsorption processes that produce an essentially carbon monoxide-free hydrogen or helium gas stream from, respectively, a high-purity (e.g., pipeline grade) hydrogen or helium gas stream using one or two adsorber beds. By using physical adsorbents with high heats of nitrogen adsorption, intermediate heats of carbon monoxide adsorption, and low heats of hydrogen and helium adsorption, and by using vacuum purging and high feed stream pressures (e.g., pressures of as high as around 1,000 bar), pipeline grade hydrogen or helium can purified to produce essentially carbon monoxide -free hydrogen and helium, or carbon monoxide, nitrogen, and methane-free hydrogen and helium.

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.

Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping

NASA Astrophysics Data System (ADS)

Lozada-Hidalgo, M.; Zhang, S.; Hu, S.; Esfandiar, A.; Grigorieva, I. V.; Geim, A. K.

2017-05-01

Thousands of tons of isotopic mixtures are processed annually for heavy-water production and tritium decontamination. The existing technologies remain extremely energy intensive and require large capital investments. New approaches are needed to reduce the industry's footprint. Recently, micrometre-size crystals of graphene are shown to act as efficient sieves for hydrogen isotopes pumped through graphene electrochemically. Here we report a fully-scalable approach, using graphene obtained by chemical vapour deposition, which allows a proton-deuteron separation factor of around 8, despite cracks and imperfections. The energy consumption is projected to be orders of magnitude smaller with respect to existing technologies. A membrane based on 30 m2 of graphene, a readily accessible amount, could provide a heavy-water output comparable to that of modern plants. Even higher efficiency is expected for tritium separation. With no fundamental obstacles for scaling up, the technology's simplicity, efficiency and green credentials call for consideration by the nuclear and related industries.

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.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

PubMed

Cirtiu, Ciprian Mihai; Hassani, Hicham Oudghiri; Bouchard, Nicolas-Alexandre; Rowntree, Paul A; Ménard, Hugues

2006-07-04

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH

Application of carbon and hydrogen stable isotope analyses to detect exogenous citric acid in Japanese apricot liqueur.

PubMed

Akamatsu, Fumikazu; Oe, Takaaki; Hashiguchi, Tomokazu; Hisatsune, Yuri; Kawao, Takafumi; Fujii, Tsutomu

2017-08-01

Japanese apricot liqueur manufacturers are required to control the quality and authenticity of their liqueur products. Citric acid made from corn is the main acidulant used in commercial liqueurs. In this study, we conducted spiking experiments and carbon and hydrogen stable isotope analyses to detect exogenous citric acid used as an acidulant in Japanese apricot liqueurs. Our results showed that the δ 13 C values detected exogenous citric acid originating from C 4 plants but not from C 3 plants. The δ 2 H values of citric acid decreased as the amount of citric acid added increased, whether the citric acid originated from C 3 or C 4 plants. Commercial liqueurs with declared added acidulant provided higher δ 13 C values and lower δ 2 H values than did authentic liqueurs and commercial liqueurs with no declared added acidulant. Carbon and hydrogen stable isotope analyses are suitable as routine methods for detecting exogenous citric acid in Japanese apricot liqueur. Copyright © 2017 Elsevier Ltd. All rights reserved.

First Principles Study of Adsorption of Hydrogen on Typical Alloying Elements and Inclusions in Molten 2219 Al Alloy

PubMed Central

Liu, Yu; Huang, Yuanchun; Jia, Guangze

2017-01-01

To better understand the effect of the components of molten 2219 Al alloy on the hydrogen content dissolved in it, the H adsorption on various positions of alloying element clusters of Cu, Mn and Al, as well as the inclusion of Al2O3, MgO and Al4C3, were investigated by means of first principles calculation, and the thermodynamic stability of H adsorbed on each possible site was also studied on the basis of formation energy. Results show that the interaction between Al, MgO, Al4C3 and H atoms is mainly repulsive and energetically unfavorable; a favorable interaction between Cu, Mn, Al2O3 and H atoms was determined, with H being more likely to be adsorbed on the top of the third atomic layer of Cu(111), the second atomic layer of Mn(111), and the O atom in the third atomic layer of Al2O3, compared with other sites. It was found that alloying elements Cu and Mn and including Al2O3 may increase the hydrogen adsorption in the molten 2219 Al alloy with Al2O3 being the most sensitive component in this regard. PMID:28773185

Carbon and Hydrogen Isotope Fractionation in Lipid Biosynthesis of Piezophilic Bacteria - Implications for Studying Microbial Metabolism and Carbon Cycle in Deep Biosphere

NASA Astrophysics Data System (ADS)

Fang, J.; Dasgupta, S.; Zhang, L.; Li, J.; Kato, C.; Bartlett, D.

2012-12-01

Piezophiles are pressure-loving microorganisms, which reproduce preferentially or exclusively at pressures greater than atmospheric pressure. In this study, we examined stable carbon and hydrogen isotope fractionation in fatty acid biosynthesis of a piezophilic bacterium Moritella japonica DSK1. The bacterium was grown to stationary phase at hydrstatic pressures of 0.1, 10, 20, and 50 MPa (mega-passcal) in media prepared using sterilized natural seawater supplied with glucose as the sole carbon source. Bacterial cell biomass and individual fatty acids exhibited consistent pressure-dependent carbon and hydrogen isotope fractionations relative to substrates. Average carbon isotope fractionation (delta(FA-glucose)) at high pressures was much higher than that for surface bacteria: -15.7, -15.3, and -18.3‰ at 10, 20, and 50 MPa, respectively. For deltaD, fatty acids are more depleted in D relative to glucose than to water. Monounsaturated fatty acids are more depleted in D than corresponding saturated fatty acids by as much as 36‰. Polyunsaturated fatty acids are most depleted in D. For example, DHA (22:6omega3) has the most negative hydrogen isotope ratio (-170.91‰) (delta(FA-glucose) = -199, delta(FA-water) = -176). The observed isotope effects can be ascribed to the kinetics of enzymatic reactions that are affected by hydrostatic pressure and to operating of two independent lipid biosynthetic pathways of the piezophilic bacteria. Given that most of the biosphere lives under high pressures, our results have important important implications for studying microbial metabolism and carbon cycle in the deep biosphere.

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.

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Natural diatomite modified as novel hydrogen storage material

NASA Astrophysics Data System (ADS)

Jin, Jiao; Zheng, Chenghui; Yang, Huaming

2014-03-01

Natural diatomite, subjected to different modifications, is investigated for hydrogen adsorption capacities at room temperature. An effective metal-modified strategy is developed to disperse platinum (Pt) and palladium (Pd) nanoparticles on the surface of diatomite. Hydrogen adsorption capacity of pristine diatomite (diatomite) is 0.463 wt.% at 2.63 MPa and 298 K, among the highest of the known sorbents, while that of acid-thermally activated diatomite (A-diatomite) could reach up to 0.833 wt.% due to the appropriate pore properties by activation. By incorporation with a small amount of Pt and Pd ( 0.5 wt.%), hydrogen adsorption capacities are enhanced to 0.696 wt.% and 0.980 wt.%, respectively, indicating that activated diatomite shows interesting application in the field of hydrogen storage at room temperature.

Hydrogen Storage in metal-modified single-walled carbon nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dr. Ahn

2004-04-30

It has been known for over thirty years that potassium-intercalated graphites can readily adsorb and desorb hydrogen at {approx}1 wt% at 77 K. These levels are much higher than can be attained in pure graphite, owing to a larger thermodynamic enthalpy of adsorption. This increased enthalpy may allow hydrogen sorption at higher temperatures. Potassium has other beneficial effects that enable the design of a new material: (a) Increased adsorption enthalpy in potassium-intercalated graphite compared to pure graphite reduces the pressure and increases the temperature required for a given fractional coverage of hydrogen adsorption. We expect the same effects in potassium-intercalatedmore » SWNTs. (b) As an intercalant, potassium separates c-axis planes in graphite. Potassium also separates the individual tubes of SWNTs ropes producing swelling and increased surface area. Increased surface area provides more adsorption sites, giving a proportionately higher capacity. The temperature of adsorption depends on the enthalpy of adsorption. The characteristic temperature is roughly the adsorption enthalpy divided by Boltzmann's constant, k{sub B}. For the high hydrogen storage capacity of SWNTs to be achieved at room temperature, it is necessary to increase the enthalpy of adsorption. Our goal for this project was to use metal modifications to the carbon surface of SWNTs in order to address both enhanced adsorption and surface area. For instance, the enthalpy of sorption of hydrogen on KC8 is 450 meV/H{sub 2}, whereas it is 38 meV/H{sub 2} for unmodified SWNTs. By adsorption thermodynamics we expect approximately that the same performance of SWNTs at 77 K will be achieved at a temperature of [450/38] 77 K = 900 K. This is a high temperature, so we expect that adsorption on nearly all the available sites for hydrogen will occur at room temperature under a much lower pressure. This pressure can be estimated conveniently, since the chemical potential of hydrogen is

Detection of hydrogen peroxide with graphyne

NASA Astrophysics Data System (ADS)

Majidi, R.; Karami, A. R.

2013-12-01

The effect of hydrogen peroxide on the electronic properties of graphyne has been investigated to explore the possibility of using graphyne based biosensor. We have used density functional theory to study the electronic properties of γ-graphyne in the presence of different number of hydrogen peroxide. The optimal adsorption position, orientation, and distance of hydrogen peroxide adsorbed on the graphyne sheet have been determined by calculating adsorption energy. It is found that γ-graphyne which is an intrinsic semiconductor becomes an n-type semiconductor due to the presence of hydrogen peroxide. The energy band gap of γ-graphyne is decreased by increasing the number of hydrogen peroxide. The results demonstrate that γ-graphyne is a promising candidate for biosensor application because of its electrical sensitivity to hydrogen peroxide.

Reconstructing hydroclimatic variations using compound-specific hydrogen isotope analysis of biomarkers from a maar lake in the Central Highlands, Vietnam

NASA Astrophysics Data System (ADS)

Doiron, K. E.; Stevens, L. R.; Sauer, P. E.

2017-12-01

Monsoonal variation in Southeast Asia affects a significant portion of the global population, but knowledge regarding response of the monsoon system to changing boundary conditions is limited. The paleoclimatic tool of compound-specific isotope analysis(CSIA) provides the ability to reconstruct past precipitation using a diverse set of biomarkers preserved in the sedimentary record. Limited proxies in tropical southeast Asia and difficult site access have led to a deficit in paleoclimate records. Ia M'He (14°10'45" N, 107°52' E) is a shallow volcanic crater (maar) lake, approximately 57 ha, located in the Central Highlands of Vietnam. Precipitation in the Central Highlands is sensitive to reorganizations of major climatic features, such as the migration of the ITCZ and the coupled Indo-Asian monsoon, ENSO and related shifts in the Pacific Walker Circulation and typhoon frequency. To examine this complex behavior, this pilot study aims to provide a 500-year record of effective moisture inferred from CSIA of hydrogen isotopes on biomarkers. This study highlights the use of hydrogen isotopes of C28 n-alkanoic acid and dominant n-alkane chain lengths of C27 and C29, associated with terrestrial plant leaf waxes, as tracers for precipitation. The hydrogen isotope ratios of the plant wax components provide a proxy for paleo precipitation in a region where rainfall and droughts heavily influence population dynamics and create social discord. The CSIA record is expected to correlate with records from northern Vietnam, the South China Sea and Indonesia, with greater precipitation during the Little Ice Age. The CSIA data of terrestrial plant leaf waxes will be compared with secondary proxies including: diatoms, C/N and biogenic silica.

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria

PubMed Central

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-01-01

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell–Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h≅1013 s−1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2′-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria.

PubMed

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-08-29

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell-Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h congruent with 10(13) s-1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2'-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature

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.

Reconstructing hydroclimatic variations using compound-specific hydrogen isotope analysis of biomarkers from a maar lake in the Central Highlands, Vietnam

NASA Astrophysics Data System (ADS)

Doiron, Kelsey; Stevens, Lora; Sauer, Peter

2017-04-01

Monsoonal variation in Southeast Asia affects a significant portion of the global population, but knowledge regarding response of the monsoon system to changing boundary conditions is limited. The paleoclimatic tool of compound-specific isotope analysis(CSIA) provides the ability to reconstruct past precipitation using a diverse set of biomarkers preserved in the sedimentary record. Limited proxies in tropical southeast Asia and difficult site access have led to a deficit in paleoclimate records. Ia M'He (14˚ 10'45" N, 107˚ 52' E) is a shallow volcanic crater (maar) lake, approximately 57 ha, located in the Central Highlands of Vietnam. Precipitation in the Central Highlands is sensitive to reorganizations of major climatic features, such as the migration of the ITCZ and the coupled Indo-Asian monsoon, ENSO and related shifts in the Pacific Walker Circulation and typhoon frequency. To examine this complex behavior, this pilot study aims to provide a 500-year record of effective moisture inferred from CSIA of hydrogen isotopes on biomarkers. Carbon/nitrogen ratios and carbon isotope ratios indicate that bulk organic matter is a combination of algae and C3 vegetation, offering the potential to use compound-specific hydrogen isotopes of aquatic and terrestrial organic matter in tandem. Preliminary analysis of the core shows dominant alkane chain lengths of C27 and C29, associated with terrestrial plant leaf waxes. The hydrogen isotope ratios of the plant wax components provide a proxy for paleo precipitation in a region where rainfall and droughts heavily influence population dynamics and create social discord. The CSIA record is expected to correlate with records from northern Vietnam, the South China Sea and Indonesia, with greater precipitation during the Little Ice Age. The degree to which evaporative modification of lake water (i.e., seasonal drying) occurs will be estimated by comparing the terrestrial CSIA values indicative of meteoric water with aquatic CSIA

Preparation of organic and water hydrogen for stable isotope analysis. Effects due to reaction vessels and zinc reagent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schimmelmann, A.; DeNiro, M.J.

1993-03-15

Combustion of organic matter in sealed Pyrex, Vycor, and quartz ampules at temperatures between 520 and 900[degrees]C yields less than stoichiometric amounts of water. The loss of hydrogen to hydration reactions between water vapor and glass/quartz interferes with the determination of C/H and N/H elemental ratios in organic matter. The effect increases from quartz to Vycor to Pyrex, but the incomplete yield does not significantly affect the precision and accuracy of the determination of stable hydrogen isotope ratios. Reactions between water and Pyrex do not affect the conversion of water to hydrogen with zinc in Pyrex ampules at 500[degrees]C, whichmore » is quantitative, but even preoutgassed zinc contains a deuterium-depleted hydrogen blank. D/H ratios in hydrogen from the Zn method require a nonlinear correction to achieve compatibility with [delta]D values from the uranium method. 19 refs., 4 tabs.« less

A ’Hydrogen Partitioning’ Model for Hydrogen Assisted Crack Growth.

DTIC Science & Technology

1984-09-01

the change in Stage II crack growth rate from Region A to Region C in the 18NI maraging steels . It cannot, however, explain the sudden drop off in...Neither partitioning of hydrogen nor adsorption equilibrium can account for the observed "high" temperature response of l8Ni maraging steel in hydrogen...ment and Stress Corrosion Cracking, American Society for Metals, Metals Park, OH, 1984, p. 103 (in press). 11. R. P. Wei: in Hydrogen Effects in

Hydrogen isotope trapping in Al-Cu binary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Paul; Karnesky, Richard A.

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 ismore » high; for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D 2 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

Hydrogen isotope trapping in Al-Cu binary alloys

DOE PAGES

Chao, Paul; Karnesky, Richard A.

2016-01-01

In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol –1 (0.19 ± 0.03 eV). Typical occupancy of this trap ismore » high; for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D 2 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

Effects of van der Waals density functional corrections on trends in furfural adsorption and hydrogenation on close-packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Liu, Bin; Cheng, Lei; Curtiss, Larry; Greeley, Jeffrey

2014-04-01

The hydrogenation of furfural to furfuryl alcohol on Pd(111), Cu(111) and Pt(111) is studied with both standard Density Functional Theory (DFT)-GGA functionals and with van der Waals-corrected density functionals. VdW-DF functionals, including optPBE, optB88, optB86b, and Grimme's method, are used to optimize the adsorption configurations of furfural, furfuryl alcohol, and related intermediates resulting from hydrogenation of furfural, and the results are compared to corresponding values determined with GGA functionals, including PW91 and PBE. On Pd(111) and Pt(111), the adsorption geometries of the intermediates are not noticeably different between the two classes of functionals, while on Cu(111), modest changes are seen in both the perpendicular distance and the orientation of the aromatic ring with respect to the planar surface. In general, the binding energies increase substantially in magnitude as a result of van der Waals contributions on all metals. In contrast, however, dispersion effects on the kinetics of hydrogenation are relatively small. It is found that activation barriers are not significantly affected by the inclusion of dispersion effects, and a Brønsted-Evans-Polanyi relationship developed solely from PW91 calculations on Pd(111) is capable of describing corresponding results on Cu(111) and Pt(111), even when the dispersion effects are included. Finally, the reaction energies and barriers derived from the dispersion-corrected and pure GGA calculations are used to plot simple potential energy profiles for furfural hydrogenation to furfuryl alcohol on the three considered metals, and an approximately constant downshift of the energetics due to the dispersion corrections is observed.

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

2016-08-09

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.

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

PubMed Central

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

2016-01-01

Hydrogen isotope (δ2H) analysis is widely used in animal ecology to study continental-scale movement because δ2H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ2H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ2H values ranging from −55‰ to +1,070‰. The δ2H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ2H among AAs was nearly 200‰. The relative distributions of δ2H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ2H of nonessential AAs varied linearly with the δ2H of media water, whereas δ2H of essential AAs was nearly identical to δ2H 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 δ2H can route directly at the molecular level. We conclude that the patterns and distributions in δ2H of AAs are determined through biosynthetic reactions, suggesting that δ2H could become a new biosignature for studying novel microbial pathways. Our results also show that δ2H of AAs in an organism’s tissues provides a dual tracer for food and environmental (e.g., drinking) water. PMID:27444017

Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy.

PubMed

Stiopkin, Igor V; Weeraman, Champika; Pieniazek, Piotr A; Shalhout, Fadel Y; Skinner, James L; Benderskii, Alexander V

2011-06-08

The air-water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth's surface and strongly affects atmospheric, aerosol and environmental chemistry. The air-water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short 'healing length' of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength. Here we report a combined experimental and theoretical study of the air-water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the 'free OD' transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

[Adsorption of Congo red from aqueous solution on hydroxyapatite].

PubMed

Zhan, Yan-Hui; Lin, Jian-Wei

2013-08-01

The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

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).

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.

Isotope composition and volume of Earth’s early oceans

PubMed Central

Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.

2012-01-01

Oxygen and hydrogen isotope compositions of Earth’s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen’s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth’s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. PMID:22392985

Electronic and optical properties of hydrogenated silicon carbide nanosheets: A DFT study

NASA Astrophysics Data System (ADS)

Delavari, Najmeh; Jafari, Mahmoud

2018-07-01

Density-functional theory has been applied to investigate the effect of hydrogen adsorption on silicon carbide (SiC) nanosheets, considering six, different configurations for adsorption process. The chair-like configuration is found to be the most stable because of the adsorption of hydrogen atoms by silicon and carbon atoms on the opposite sides. The pure and hydrogenated SiC monolayers are also found to be sp2- and sp3-hybridized, respectively. The binding energy of the hydrogen atoms in the chair-like structure is calculated about -3.845 eV, implying the system to be much more stable than the same study based on graphene, though with nearly the same electronic properties, strongly proposing the SiC monolayer to be a promising material for next generation hydrogen storage. Optical properties presented in terms of the real and the imaginary parts of the dielectric function also demonstrate a decrease in the dielectric constant and the static refractive index due to hydrogen adsorption with the Plasmon frequency of the chair-like, hydrogenated monolayer, occurring at higher energies compared to that of the pure one.

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.

Stable-isotope ratios of hydrogen and oxygen in precipitation at Norman, Oklahoma, 1996-2008

USGS Publications Warehouse

Jaeschke, Jeanne B.; Scholl, Martha A.; Cozzarelli, Isabelle M.; Masoner, Jason R.; Christenson, Scott; Qi, Haiping

2011-01-01

Precipitation samples for measurement of stable-isotope ratios of hydrogen (delta2H) and oxygen (delta18O) were collected at the Norman Landfill Research Site in Norman, Oklahoma, from May 1996 to October 2008. Rainfall amounts also were measured at the site (U.S. Geological Survey gaging station 07229053) during the collection period. The delta2H of precipitation samples ranged from -121.9 to +8.3 per mil, and the delta18O of precipitation ranged from -16.96 to +0.50 per mil. The volume-weighted average values for delta2H and delta18O of precipitation over the 12-year measurement period were -31.13 per mil for delta2H and -5.57 per mil for delta18O. Average summer-season delta2H and delta18O values of precipitation usually were more positive (enriched in the heavier isotopes) than winter values.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-09-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-04-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb/ppb and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2/ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Comparative study of hydrogen storage on metal doped mesoporous materials

NASA Astrophysics Data System (ADS)

Carraro, P. M.; Sapag, K.; Oliva, M. I.; Eimer, G. A.

2018-06-01

The hydrogen adsorption capacity of mesoporous materials MCM-41 modified with Co, Fe, Ti, Mg and Ni at 77 K and 10 bar was investigated. Various techniques including XRD, N2 adsorption and DRUV-vis were employed for the materials characterization. The results showed that a low nickel loading on MCM-41 support promoted the presence of hydrogen-favorable sites, increasing the hydrogen storage capacity.

Hydrogen isotope geochemistry and heat balance of a fumarolic system: Kudriavy volcano, Kuriles

NASA Astrophysics Data System (ADS)

Botcharnikov, Roman E.; Shmulovich, Kirill I.; Tkachenko, Sergey I.; Korzhinsky, Mikhail A.; Rybin, Alexander V.

2003-05-01

The temperature and hydrogen isotope composition of the fumarolic gases have been studied at Kudriavy volcano, Kurile Islands, which is unique for investigating the processes of magma degassing because of the occurrence of numerous easily accessible fumaroles with a temperature range of 100-940°C. There are several local fumarolic fields with a total surface area of about 2600 m 2 within the flattened crater of 200×600 m. Each fumarolic field is characterized by the occurrence of high- and low-temperature fumaroles with high gas discharges and steaming areas with lower temperatures. We have studied the thermal budget of the Kudriavy fumarolic system on the basis of the quantitative dependences of the hydrogen isotope ratio (D/H) and tritium concentration on the temperature of fumarolic gases and compared them with the calculated heat balance of mixing between hot magmatic gas and cold meteoric water. Hydrogen isotope composition (δD and 3H) shows a well expressed correlation with the gas temperature. Since D/H ratio and 3H are good indicators of water sources in volcanic areas, it suggests that the thermal budget of the fumarolic system is mostly controlled by the admixing of meteoric waters to magmatic gases. The convective mechanism of heat transfer in the hydrothermal system governs the maximum temperatures of local fumaroles and fumarolic fields. Low-temperature fumaroles at Kudriavy are thermally buffered by the boiling processes of meteoric waters in the mixing zone at pressures of 3-12 bar. These values may correspond to the hydrostatic pressure of water columns about 30-120 m in height in the volcanic edifice and hence to the depth of a mixing/boiling zone. Conductive heat transfer is governed by conductive heat exchange between gases and country rocks and appears to be responsible for the temperature distribution around a local fumarolic vent. The temperature and pressure of shallow degassing magma are estimated to be 1050°C and 2-3 bar, respectively

Separation of sulfur isotopes

DOEpatents

DeWitt, Robert; Jepson, Bernhart E.; Schwind, Roger A.

1976-06-22

Sulfur isotopes are continuously separated and enriched using a closed loop reflux system wherein sulfur dioxide (SO.sub.2) is reacted with sodium hydroxide (NaOH) or the like to form sodium hydrogen sulfite (NaHSO.sub.3). Heavier sulfur isotopes are preferentially attracted to the NaHSO.sub.3, and subsequently reacted with sulfuric acid (H.sub.2 SO.sub.4) forming sodium hydrogen sulfate (NaHSO.sub.4) and SO.sub.2 gas which contains increased concentrations of the heavier sulfur isotopes. This heavy isotope enriched SO.sub.2 gas is subsequently separated and the NaHSO.sub.4 is reacted with NaOH to form sodium sulfate (Na.sub.2 SO.sub.4) which is subsequently decomposed in an electrodialysis unit to form the NaOH and H.sub.2 SO.sub.4 components which are used in the aforesaid reactions thereby effecting sulfur isotope separation and enrichment without objectionable loss of feed materials.

Molybdenum isotope fractionation during complexation with organic matter in the Critical Zone

NASA Astrophysics Data System (ADS)

King, E. K.; Pett-Ridge, J. C.; Perakis, S. S.

2016-12-01

Molybdenum (Mo) is a micronutrient and a redox sensitive trace metal that also forms strong complexes with organic matter (OM). The fractionation of Mo in sediments associated with adsorption onto both iron (Fe) and manganese (Mn) (oxyhydr)oxides under oxic conditions and sulfide phases under euxinic conditions has been used to constrain redox conditions in the ocean. Additionally, Mo isotope dynamics in terrestrial systems can shed light on the pedogenic mechanisms driving the riverine Mo isotopic composition and how atmospheric inputs alter the trace metal budget and isotopic composition of soils. As a result of these studies, it has been hypothesized that multiple mechanisms are responsible for fractionating Mo isotopes. In particular, Mo fractionation during adsorption onto OM is unknown, despite the fact this mechanism is 3x to more than 20x greater than adsorption onto Fe- and Mn- (oxyhydr)oxides across a range of soil types from Oregon, Iceland, and Hawaii1-3 (Marks et al., 2015; Siebert et al., 2015; King et al., 2016). In this study, we measured Mo adsorption and isotopic fractionation onto insolubilized humic acid (IHA), a proxy for OM, as a function of both adsorption time (2-170 h) and pH (2-7). Preliminary results suggest that for the time series experiment, Mo adsorption onto IHA increased from 35% to 64% and a plateau was reached after 24 hours. The average Mo isotope fractionation between the solution and the IHA was Δ98Mosolution-IHA = 1.8 ± 0.3‰. For the pH series experiment, the average Mo isotope fractionation was Δ98Mosolution-IHA = 2.0 ± 0.2‰. Next, we compared the Mo isotopic composition of foliage, O-horizon, and surface soil from 12 sites in the Oregon Coast Range to better understand the impact of OM on Mo isotope dynamics in natural samples. The potential isotopic offset between dissolved and adsorbed Mo onto OM is of the same order of magnitude and direction as fractionation onto Fe- and Mn- (oxyhydr)oxides such as ferrihydrite

Investigation of the microbial metabolism of carbon dioxide and hydrogen in the kangaroo foregut by stable isotope probing

PubMed Central

Godwin, Scott; Kang, Alicia; Gulino, Lisa-Maree; Manefield, Mike; Gutierrez-Zamora, Maria-Luisa; Kienzle, Marco; Ouwerkerk, Diane; Dawson, Kerri; Klieve, Athol V

2014-01-01

Kangaroos ferment forage material in an enlarged forestomach analogous to the rumen, but in contrast to ruminants, they produce little or no methane. The objective of this study was to identify the dominant organisms and pathways involved in hydrogenotrophy in the kangaroo forestomach, with the broader aim of understanding how these processes are able to predominate over methanogenesis. Stable isotope analysis of fermentation end products and RNA stable isotope probing (RNA-SIP) were used to investigate the organisms and biochemical pathways involved in the metabolism of hydrogen and carbon dioxide in the kangaroo forestomach. Our results clearly demonstrate that the activity of bacterial reductive acetogens is a key factor in the reduced methane output of kangaroos. In in vitro fermentations, the microbial community of the kangaroo foregut produced very little methane, but produced a significantly greater proportion of acetate derived from carbon dioxide than the microbial community of the bovine rumen. A bacterial operational taxonomic unit closely related to the known reductive acetogen Blautia coccoides was found to be associated with carbon dioxide and hydrogen metabolism in the kangaroo foregut. Other bacterial taxa including members of the genera Prevotella, Oscillibacter and Streptococcus that have not previously been reported as containing hydrogenotrophic organisms were also significantly associated with metabolism of hydrogen and carbon dioxide in the kangaroo forestomach. PMID:24621520

Investigation of the microbial metabolism of carbon dioxide and hydrogen in the kangaroo foregut by stable isotope probing.

PubMed

Godwin, Scott; Kang, Alicia; Gulino, Lisa-Maree; Manefield, Mike; Gutierrez-Zamora, Maria-Luisa; Kienzle, Marco; Ouwerkerk, Diane; Dawson, Kerri; Klieve, Athol V

2014-09-01

Kangaroos ferment forage material in an enlarged forestomach analogous to the rumen, but in contrast to ruminants, they produce little or no methane. The objective of this study was to identify the dominant organisms and pathways involved in hydrogenotrophy in the kangaroo forestomach, with the broader aim of understanding how these processes are able to predominate over methanogenesis. Stable isotope analysis of fermentation end products and RNA stable isotope probing (RNA-SIP) were used to investigate the organisms and biochemical pathways involved in the metabolism of hydrogen and carbon dioxide in the kangaroo forestomach. Our results clearly demonstrate that the activity of bacterial reductive acetogens is a key factor in the reduced methane output of kangaroos. In in vitro fermentations, the microbial community of the kangaroo foregut produced very little methane, but produced a significantly greater proportion of acetate derived from carbon dioxide than the microbial community of the bovine rumen. A bacterial operational taxonomic unit closely related to the known reductive acetogen Blautia coccoides was found to be associated with carbon dioxide and hydrogen metabolism in the kangaroo foregut. Other bacterial taxa including members of the genera Prevotella, Oscillibacter and Streptococcus that have not previously been reported as containing hydrogenotrophic organisms were also significantly associated with metabolism of hydrogen and carbon dioxide in the kangaroo forestomach.

A Novel Framework for Quantifying past Methane Recycling by Sphagnum-Methanotroph Symbiosis Using Carbon and Hydrogen Isotope Ratios of Leaf Wax Biomarkers

NASA Technical Reports Server (NTRS)

Nichols, Jonathan E.; Isles, Peter D. F.; Peteet, Dorothy M.

2014-01-01

The concentration of atmospheric methane is strongly linked to variations in Earth's climate. Currently, we can directly reconstruct the total atmospheric concentration of methane, but not individual terms of the methane cycle. Northern wetlands, dominated by Sphagnum, are an important contributor of atmospheric methane, and we seek to understand the methane cycle in these systems. We present a novel method for quantifying the proportion of carbon Sphagnum assimilates from its methanotrophic symbionts using stable isotope ratios of leaf-wax biomarkers. Carbon isotope ratios of Sphagnum compounds are determined by two competing influences, water content and the isotope ratio of source carbon. We disentangled these effects using a combined hydrogen and carbon isotope approach. We constrained Sphagnum water content using the contrast between the hydrogen isotope ratios of Sphagnum and vascular plant biomarkers. We then used Sphagnum water content to calculate the carbon isotope ratio of Sphagnum's carbon pool. Using a mass balance equation, we calculated the proportion of recycled methane contributed to the Sphagnum carbon pool, 'PRM.' We quantified PRM in peat monoliths from three microhabitats in the Mer Bleue peatland complex. Modern studies have shown that water table depth and vegetation have strong influences on the peatland methane cycle on instrumental time scales. With this new approach, delta C-13 of Sphagnum compounds are now a useful tool for investigating the relationships among hydrology, vegetation, and methanotrophy in Sphagnum peatlands over the time scales of entire peatland sediment records, vital to our understanding of the global carbon cycle through the Late Glacial and Holocene.

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.;

Interaction of hydrogen with palladium clusters deposited on graphene

NASA Astrophysics Data System (ADS)

Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J.

2015-12-01

Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H2 on Pd6 anchored on a graphene vacancy has been studied in detail.

Probing the Structure, Stability and Hydrogen Adsorption of Lithium Functionalized Isoreticular MOF-5 (Fe, Cu, Co, Ni and Zn) by Density Functional Theory

PubMed Central

Venkataramanan, Natarajan Sathiyamoorthy; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2009-01-01

Li adsorption on isoreticular MOFs with metal Fe, Cu, Co, Ni and Zn was studied using density function theory. Li functionalization shows a considerable structural change associated with a volume change in isoreticular MOF-5 except for the Zn metal center. Hydrogen binding energies on Li functionalized MOFs are seen to be in the range of 0.2 eV, which is the desired value for an ideal reversible storage system. This study has clearly shown that Li doping is possible only in Zn-based MOF-5, which would be better candidate to reversibly store hydrogen. PMID:19468328

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.

Some notes on hydrogen-related point defects and their role in the isotope exchange and electrical conductivity in olivine

NASA Astrophysics Data System (ADS)

Karato, Shun-ichiro

2015-11-01

Nominally anhydrous minerals such as olivine dissolve hydrogen in a variety of forms including free (or interstitial) proton (Hrad) and two protons trapped at the M-site ((2 H)M×). The strength of chemical bonding between protons and the surrounding atoms are different among different species, and consequently protons belonging to different species likely have different mobility (diffusion coefficients). I discuss the role of diffusion of protons in different species in the isotope exchange and hydrogen-assisted electrical conductivity adding a few notes to the previous work by Karato (2013) including a new way to test the model. I conclude that in the case of isotope exchange, the interaction among these species is strong because diffusion is heterogeneous, whereas there is no strong interaction among different species in electrical conduction where diffusion is homogeneous (in an infinite crystal). Consequently, the slowest diffusing species controls the rate of isotope exchange, whereas the fastest diffusing species controls electrical conductivity leading to a different temperature dependence of activation energy and anisotropy. This model explains the differences in the activation energy and anisotropy between isotope diffusion and electrical conductivity, and predicts that the mechanism of electrical conductivity changes with temperature providing an explanation for most of the discrepancies among different experimental observations at different temperatures except for those by Poe et al. (2010) who reported anomalously high water content dependence and highly anisotropic activation energy. When the results obtained at high temperatures are used, most of the geophysically observed high and highly anisotropic electrical conductivity in the asthenosphere can be explained without invoking partial melting.

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

NASA Astrophysics Data System (ADS)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

Microscale Enhancement of Heat and Mass Transfer for Hydrogen Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drost, Kevin; Jovanovic, Goran; Paul, Brian

2015-09-30

The document summarized the technical progress associated with OSU’s involvement in the Hydrogen Storage Engineering Center of Excellence. OSU focused on the development of microscale enhancement technologies for improving heat and mass transfer in automotive hydrogen storage systems. OSU’s key contributions included the development of an extremely compact microchannel combustion system for discharging hydrogen storage systems and a thermal management system for adsorption based hydrogen storage using microchannel cooling (the Modular Adsorption Tank Insert or MATI).

Adsorption and dissociation of molecular hydrogen on orthorhombic β-Mo 2C and cubic δ-MoC (001) surfaces

DOE PAGES

Posada-Pérez, Sergio; Viñes, Francesc; Valero, Rosendo; ...

2016-10-03

Molybdenum carbides are increasingly used in heterogeneously catalyzed hydrogenation reactions, which imply the adsorption and dissociation of molecular hydrogen. In this paper, a systematic density functional theory based study, including or excluding dispersion terms, concerning the interaction and stability of H 2 with cubic δ-MoC(001) and orthorhombic β-Mo 2C(001) surfaces, is presented. In the latter case the two possible C or Mo terminations are considered. In addition, different situations for the H covered surfaces are examined. Computational results including dispersive forces predict an essentially spontaneous dissociation of H 2 on β-Mo 2C(001) independently of the surface termination, whereas on δ-MoC(001)more » molecular hydrogen dissociation implies a small but noticeable energy barrier. Furthermore, the ab initio thermodynamics formalism has been used to compare the stability of different H coverages. In conclusion, core level binding energies and vibrational frequencies are presented with the aim to assist the interpretation of yet unavailable data from X-ray photoelectron and infrared spectroscopies.« less

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range.

PubMed

Liu, Jingfeng; Xiao, Cunde; Ding, Minghu; Ren, Jiawen

2014-11-01

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of δ(18)O and δ(2)H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature (Tair), with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial-temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world. Copyright © 2014. Published by Elsevier B.V.

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal

Hydrogen production from food wastes and gas post-treatment by CO{sub 2} adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Redondas, V.; Gomez, X., E-mail: xagomb@unileon.es; Garcia, S.

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 formore » 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

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

USGS Publications Warehouse

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

2017-01-01

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

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.

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

Variation in catchment areas of Indiana bat (Myotis sodalis) hibernacula inferred from stable hydrogen (δ2H) isotope analysis.

Treesearch

E.R. Britzke; S.C. Loeb; C.S. Romanek; K.A. Hobson; M.J. Vonhof

2013-01-01

Understanding seasonal movements of bats is important for effective conservation efforts. Although female Indiana bats (Myotis sodalis Miller and Allen, 1928) have been documented to migrate >500 km, knowledge of their migratory patterns is still extremely limited. We used the relationship between latitude and stable hydrogen isotope ratio in bat hair (δ...

Antibody adsorption on the surface of water studied by neutron reflection

PubMed Central

Li, Zongyi; Holman, Robert; Pan, Fang; Campbell, Richard A.; Campana, Mario; Li, Peixun; Webster, John R. P.; Bishop, Steven; Narwal, Rojaramani; Uddin, Shahid

2017-01-01

ABSTRACT Surface and interfacial adsorption of antibody molecules could cause structural unfolding and desorbed molecules could trigger solution aggregation, resulting in the compromise of physical stability. Although antibody adsorption is important and its relevance to many mechanistic processes has been proposed, few techniques can offer direct structural information about antibody adsorption under different conditions. The main aim of this study was to demonstrate the power of neutron reflection to unravel the amount and structural conformation of the adsorbed antibody layers at the air/water interface with and without surfactant, using a monoclonal antibody ‘COE-3′ as the model. By selecting isotopic contrasts from different ratios of H2O and D2O, the adsorbed amount, thickness and extent of the immersion of the antibody layer could be determined unambiguously. Upon mixing with the commonly-used non-ionic surfactant Polysorbate 80 (Tween 80), the surfactant in the mixed layer could be distinguished from antibody by using both hydrogenated and deuterated surfactants. Neutron reflection measurements from the co-adsorbed layers in null reflecting water revealed that, although the surfactant started to remove antibody from the surface at 1/100 critical micelle concentration (CMC) of the surfactant, complete removal was not achieved until above 1/10 CMC. The neutron study also revealed that antibody molecules retained their globular structure when either adsorbed by themselves or co-adsorbed with the surfactant under the conditions studied. PMID:28353420

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, John D.; Meikrantz, David H.; Tuggle, Dale G.

1997-01-01

A method and apparatus for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes.

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, J.D.; Meikrantz, D.H.; Tuggle, D.G.

1997-09-23

A method and apparatus are disclosed for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes. 15 figs.

Caution on the use of NBS 30 biotite for hydrogen-isotope measurements with on-line high-temperature conversion systems

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Olack, Gerard; Vennemann, Torsten W.

2014-01-01

RATIONALEThe supply of NBS 30 biotite is nearly exhausted. During measurements of NBS 30 and potential replacements, reproducible δ2HVSMOW-SLAP values could not be obtained by three laboratories using high-temperature conversion (HTC) systems. The cause of this issue has been investigated using the silver-tube technique for hydrogen-isotope measurements of water.METHODSThe δ2HVSMOW-SLAP values of NBS 30 biotite, other biotites, muscovites, and kaolinite with different particle sizes, along with IAEA-CH-7 polyethylene, and reference waters and NBS 22 oil that were sealed in silver-tube segments, were measured. The effect of absorbed water on mineral surfaces was investigated with waters both enriched and depleted in 2H. The quantitative conversion of hydrogen from biotite into gaseous hydrogen as a function of mass and particle size was also investigated.RESULTSThe δ2HVSMOW-SLAP values of NBS 30 obtained by three laboratories were as much as 21 ‰ too high compared with the accepted value of −65.7 ‰, determined by conventional off-line measurements. The experiments showed a strong correlation between grain size and the δ2HVSMOW-SLAP value of NBS 30 biotite, but not of biotites with lower iron content. The δ2HVSMOW-SLAP values of NBS 30 as a function of particle size show a clear trend toward −65.7 ‰ with finer grain size.CONCLUSIONSDetermination of the δ2HVSMOW-SLAP values of hydrous minerals and of NBS 30 biotite by on-line HTC systems coupled to isotope-ratio mass spectrometers may be unreliable because hydrogen in this biotite may not be converted quantitatively into molecular hydrogen. Extreme caution in the use and interpretation of δ2HVSMOW-SLAP on-line measurements of hydrous minerals is recommended.

New nanosized catalytic membrane reactors for hydrogenation with stored hydrogen: Prerequisites and the experimental basis for their creation

NASA Astrophysics Data System (ADS)

Soldatov, A. P.; Tsodikov, M. V.; Parenago, O. P.; Teplyakov, V. V.

2010-12-01

The prerequisites and prospects for creating a new generation of nanosized membrane reactors are considered. For the first time, hydrogenation reactions take place in ceramic membrane pores with hydrogen adsorbed beforehand in mono- and multilayered oriented carbon nanotubes with graphene walls (OCNTGs) formed on the internal pore surface. It is shown for Trumem microfiltration membranes with D avg ˜130 nm that oxidation reactions of CO on a Cu0.03Ti0.97O2 ± δ catalyst and the oxidative conversion of methane into synthesis gas and light hydrocarbons on La + Ce/MgO are considerably enhanced when they occur in membranes. Regularities of hydrogen adsorption, storage, and desorption in nanosized membrane reactors are investigated through OCNTG formation in Trumem ultrafiltration membrane pores with D avg = 50 and 90 nm and their saturation with hydrogen at a pressure of 10-13 MPa. It is shown that the amount of adsorbed hydrogen reaches 14.0% of OCNTG mass. Using thermogravimetric analysis in combination with mass-spectrometric analysis, hydrogen adsorption in OCNTG is first determined and its desorption is found to proceed at atmospheric pressure at a temperature of ˜175°C. It is shown that adsorbed hydrogen affects the transport properties of the membranes, reducing their efficiency with respect to liquids by 4-26 times. This is indirect confirmation of its high activity, due apparently the dissociative mechanism of adsorption.

Synthetic use of the primary kinetic isotope effect in hydrogen atom transfer 2: generation of captodatively stabilised radicals.

PubMed

Wood, Mark E; Bissiriou, Sabine; Lowe, Christopher; Windeatt, Kim M

2013-04-28

Using C-3 di-deuterated morpholin-2-ones bearing N-2-iodobenzyl and N-3-bromobut-3-enyl radical generating groups, only products derived from the more stabilised C-3, rather than the less stabilised C-5 translocated radicals, were formed after intramolecular 1,5-hydrogen atom transfer, suggesting that any kinetic isotope effect present was not sufficient to offset captodative stabilisation.

Deciphering the "chemical" nature of the exotic isotopes of hydrogen by the MC-QTAIM analysis: the positively charged muon and the muonic helium as new members of the periodic table.

PubMed

Goli, Mohammad; Shahbazian, Shant

2014-04-14

This report is a primarily survey on the chemical nature of some exotic species containing the positively charged muon and the muonic helium, i.e., the negatively charged muon plus helium nucleus, as exotic isotopes of hydrogen, using the newly developed multi-component quantum theory of atoms in molecules (MC-QTAIM) analysis, employing ab initio non-Born-Oppenhiemer wavefunctions. Accordingly, the "atoms in molecules" analysis performed on various asymmetric exotic isotopomers of the hydrogen molecule, recently detected experimentally [Science, 2011, 331, 448], demonstrates that both the exotic isotopes are capable of forming atoms in molecules and retaining the identity of hydrogen atoms. Various derived properties of atomic basins containing the muonic helium cast no doubt that apart from its short life time, it is a heavier isotope of hydrogen while the properties of basins containing the positively charged muon are more remote from those of the orthodox hydrogen basins, capable of appreciable donation of electrons as well as large charge polarization. However, with some tolerance, they may also be categorized as hydrogen basins though with a smaller electronegativity. All in all, the present study also clearly demonstrates that the MC-QTAIM analysis is an efficient approach to decipher the chemical nature of species containing exotic constituents, which are difficult to elucidate by experimental and/or alternative theoretical schemes.

A combined radio- and stable-isotopic study of a California coastal aquifer system

USGS Publications Warehouse

Swarzenski, Peter W.; Baskaran, Mark; Rosenbauer, Robert J.; Edwards, Brian D.; Land, Michael

2013-01-01

Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ18O), dissolved inorganic carbon (δ13CDIC), and radioactive isotopes (3H, 222Rn and 223,224,226,228Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl− concentrations attained seawater-like values and in conjunction with isotopically heavier δ18O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ13CDIC in the absence of SO42− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234U/238U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer

[Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

PubMed

Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

2014-01-01

The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasmaisotopic composition, aimed at reducing the level of heavy non-radioactive atoms will

Organic matter in primitive meteorites: a study of the hydrogen isotopic distribution in CM-type carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Piani, L.; Yurimoto, H.; Remusat, L.; Gonzales, A.; Marty, B.

2017-12-01

Chondrite meteorites are fragments of rocks coming from small bodies of the asteroid belt and constitute witnesses of the volatile-rich reservoirs present in the inner protoplanetary disk. Among these meteorites, carbonaceous chondrites contain the largest quantity of water and organic matter and are one of the most probable candidates for the delivery of water and molecular origin of life to Earth. Organic matter in carbonaceous chondrites is intimately mixed with hydrated minerals challenging its in situ characterization and the determination of its H-isotope composition (Le Guillou et al., GCA 131, 2014). Organic matter occurs as soluble components (in water or organic solvents) and an insoluble macromolecule. The insoluble organic matter (IOM) is efficiently isolated after acid leaching of the chondrite minerals. IOM has thus been investigated by a large set of analytical techniques allowing its structural organization, chemical composition and isotopic composition to be determined at several scales (e.g. Derenne and Robert, MAPS 45, 2010). In the soluble counterpart (SOM), targeted studies have shown large ranges of D/H ratios in the different classes of soluble organic compounds (i.e. carboxylic acids, ketones and aldehydes, amino-acids etc.) (Remusat, Planetary Mineralogy 15, 2015 and references therein). This D/H distribution indicates a complex and probably multiple-stage synthesis of this organic compounds occurring at different stages of the disk evolution. Nevertheless, inventories of the known C-bearing species in carbonaceous chondrites (carbonates, SOM and IOM) show that about 40-50 % of the carbon is hidden within the matrix (Alexander et al., MAPS 50, 2015). In this study, we perform in situ hydrogen isotope analyses at the micrometer scale by secondary ion mass spectrometry to investigate the distribution of organic matter in primitive chondrites without the use of any chemical treatment. Correlated analyses of the D/H and C/H ratios allow us to

Hydrogen rotation-vibration oscillator

DOEpatents

Rhodes, C.K.

1974-01-29

A laser system is described wherein molecular species of hydrogen and hydrogen isotopes are induced to oscillate on rotational-vibrational levels by subjecting the hydrogen to a transverse beam of electrons of a narrowly defined energy between about 1 and 5 eV, thereby producing high intensity and high energy output. (Official Gazette)

Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

NASA Astrophysics Data System (ADS)

Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

2011-12-01

Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

Molybdenum isotopes in modern marine hydrothermal Fe/Mn deposits: Implications for Archean and Paleoproterozoic Mo cycles

NASA Astrophysics Data System (ADS)

Goto, K. T.; Hein, J. R.; Shimoda, G.; Aoki, S.; Ishikawa, A.; Suzuki, K.; Gordon, G. W.; Anbar, A. D.

2016-12-01

Molybdenum isotope (δ98/95Mo) variations recorded in Archean and Paleoproterozoic Fe/Mn-rich sediments have been used to constrain ocean redox conditions at the time of deposition (Canfield et al., 2013 PNAS; Planavsky et al., 2014 Nat. Geo.; Kurzweil et al., 2015 GCA). However, except for hydrogenous Fe-Mn crusts (Siebert et al., 2003), δ98/95Mo variation of modern Fe and Mn oxide deposits has been poorly investigated. Marine hydrothermal systems are thought to be the major source of Fe and Mn in Archean and Paleoproterozoic Fe- and Mn-rich sediments. Hence, to accurately interpret Mo isotope data of those ancient sedimentary rocks, it is important to evaluate the possible influence of hydrothermally derived Mo on δ98/95Mo of modern Fe- and Mn-rich sediments. In this study, we analyzed Mo isotopic compositions of one hydrothermal Fe oxide and 15 Mn oxides from five different hydrothermal systems in the modern ocean. The Fe oxide is composed mainly of goethite, and has a δ98/95Mo of 0.7‰, which is 1.4‰ lighter than that of present-day seawater. The observed offset is similar to isotope fractionation observed during adsorption experiments of Mo on goethite (Δ98/95Mogoethite-solution = -1.4 ± 0.5%; Goldberg et al., 2009 GCA). The 15 hydrothermal Mn oxides show large variations in δ98/95Mo ranging from -1.7 to 0.5‰. However, most of the values are similar to those of modern hydrogenous Fe-Mn crusts (Siebert et al., 2003 EPSL), and fall within the range of estimated δ98/95Mo of Mn oxides precipitated from present-day seawater using the isotope offset reported from adsorption experiments (Δ98/95Mo = -2.7 ± 0.3‰; Wasylenki et al., 2008 GCA). These findings indicate that seawater is the dominant source of Mo for modern hydrothermal Fe and Mn deposits. However, the observed large variation indicates that the contribution Mo from local hydrothermal systems is not negligible. The oceanic Mo inventory during the Archean and Paleoproterozoic is thought to be

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.

Review of hydrogen storage in inorganic fullerene-like nanotubes

NASA Astrophysics Data System (ADS)

Chen, J.; Wu, F.

Following the discovery of carbon nanotubes, inorganic fullerene-like nanotubes such as WS2-MoS2, NbS2, TiS2, and BN were reported. Inorganic (non-carbon) nanotubes constitute an important class of nanomaterials with interesting properties and potential applications. As known, efficient hydrogen storage is one key problem in the development of a hydrogen energy system. Hydrogen storage using carbon nanostructures is scientifically interesting and challenging. It thus would be worthwhile to look into hydrogen storage in inorganic nanotubes because the van der Waals gaps between the nanotube layers are potential candidates for hydrogen uptake. Furthermore, the inorganic nanotubes combine two elements, which is different from the pure carbon nanotubes. These may show a novel hydrogen adsorption-desorption mechanism. The present review provides a brief study of hydrogen adsorption on MoS2, TiS2, and BN nanotubes.

Noncatalytic hydrogenation of decene-1 with hydrogen accumulated in a hybrid carbon nanostructure in nanosized membrane reactors

NASA Astrophysics Data System (ADS)

Soldatov, A. P.

2014-08-01

Studies on the creation of nanosized membrane reactors (NMRs) of a new generation with accumulated hydrogen and a regulated volume of reaction zone were continued at the next stage. Hydrogenation was performed in the pores of ceramic membranes with hydrogen preliminarily adsorbed in mono- and multilayered orientated carbon nanotubes with graphene walls (OCNTGs)—a new hybrid carbon nanostructure formed on the inner pore surface. Quantitative determination of hydrogen adsorption in OCNTGs was performed using TRUMEM ultrafiltration membranes with D av = 50 and 90 nm and showed that hydrogen adsorption was up to ˜1.5% of the mass of OCNTG. The instrumentation and procedure for noncatalytic hydrogenation of decene-1 at 250-350°C using hydrogen accumulated and stored in OCNTG were developed. The conversion of decene-1 into decane was ˜0.2-1.8% at hydrogenation temperatures of 250 and 350°C, respectively. The rate constants and activation energy of hydrogenation were determined. The latter was found to be 94.5 kJ/mol, which is much smaller than the values typical for noncatalytic hydrogenations and very close to the values characteristic for catalytic reactions. The quantitative distribution of the reacting compounds in each pore regarded as a nanosized membrane reactor was determined. The activity of hydrogen adsorbed in a 2D carbon nanostructure was evaluated. Possible mechanisms of noncatalytic hydrogenation were discussed.

Observations of Hydrogen and Oxygen Isotopes in Leaf Water Confirm the Craig-Gordon Model under Wide-Ranging Environmental Conditions1

PubMed Central

Roden, John S.; Ehleringer, James R.

1999-01-01

The Craig-Gordon evaporative enrichment model of the hydrogen (δD) and oxygen (δ18O) isotopes of water was tested in a controlled-environment gas exchange cuvette over a wide range (400‰ δD and 40‰ δ18O) of leaf waters. (Throughout this paper we use the term “leaf water” to describe the site of evaporation, which should not be confused with “bulk leaf water” a term used exclusively for uncorrected measurements obtained from whole leaf water extractions.) Regardless of how the isotopic composition of leaf water was achieved (i.e. by changes in source water, atmospheric vapor δD or δ18O, vapor pressure gradients, or combinations of all three), a modified version of the Craig-Gordon model was shown to be sound in its ability to predict the δD and δ18O values of water at the site of evaporation. The isotopic composition of atmospheric vapor was shown to have profound effects on the δD and δ18O of leaf water and its influence was dependent on vapor pressure gradients. These results have implications for conditions in which the isotopic composition of atmospheric vapor is not in equilibrium with source water, such as experimental systems that grow plants under isotopically enriched water regimes. The assumptions of steady state were also tested and found not to be a major limitation for the utilization of the leaf water model under relatively stable environmental conditions. After a major perturbation in the δD and δ18O of atmospheric vapor, the leaf reached steady state in approximately 2 h, depending on vapor pressure gradients. Following a step change in source water, the leaf achieved steady state in 24 h, with the vast majority of changes occurring in the first 3 h. Therefore, the Craig-Gordon model is a useful tool for understanding the environmental factors that influence the hydrogen and oxygen isotopic composition of leaf water as well as the organic matter derived from leaf water. PMID:10444100

Kinetic Isotope Effects as a Probe of Hydrogen Transfers to and from Common Enzymatic Cofactors

PubMed Central

Roston, Daniel; Islam, Zahidul; Kohen, Amnon

2013-01-01

Enzymes use a number of common cofactors as sources of hydrogen to drive biological processes, but the physics of the hydrogen transfers to and from these cofactors is not fully understood. Researchers study the mechanistically important contributions from quantum tunneling and enzyme dynamics and connect those processes to the catalytic power of enzymes that use these cofactors. Here we describe some progress that has been made in studying these reactions, particularly through the use of kinetic isotope effects (KIEs). We first discuss the general theoretical framework necessary to interpret experimental KIEs, and then describe practical uses for KIEs in the context of two case studies. The first example is alcohol dehydrogenase, which uses a nicotinamide cofactor to catalyze a hydride transfer, and the second example is thymidylate synthase, which uses a folate cofactor to catalyze both a hydride and a proton transfer. PMID:24161942

Experimental investigation and DFT calculation of different amine/ammonium salts adsorption on kaolinite

NASA Astrophysics Data System (ADS)

Chen, Jun; Min, Fan-fei; Liu, Lingyun; Liu, Chunfu; Lu, Fangqin

2017-10-01

The adsorption of four different amine/ammonium salts of DDA (Dodecyl amine), MDA (N-methyldodecyl amine), DMDA (N,N-dimethyldodecyl amine) and DTAC (Dodecyl trimethyl ammonium chloride) on kaolinite particles was investigated in the study through the measurement of contact angles, zeta potentials, aggregation observation, adsorption and sedimentation. The results show that different amine/ammonium salts can adsorb on the kaolinite surface to enhance the hydrophobicity and reduce the electronegativity of kaolinite particle surface, and thus induce a strong hydrophobic aggregation of kaolinite particles which promotes the settlement of kaolinite. To explore the adsorption mechanism of these four amine/ammonium salts on kaolinite surfaces, the adsorptions of DDA+, MDA+, DMDA+ and DTAC+ on kaolinite (001) surface and (00 1 bar) surface are calculated with DFT (Density functional theory). The DFT calculation results indicate that different amine/ammonium cations can strongly adsorbed on kaolinite (001) surface and (00 1 bar) surface by forming Nsbnd H⋯O strong hydrogen bonds or Csbnd H⋯O weak hydrogen bonds, and there are strongly electrostatic attractions between different amine/ammonium cations and kaolinite surfaces. The main adsorption mechanism of amine/ammonium cations on kaolinite is hydrogen-bond interaction and electrostatic attraction.

The effect of redox treatment on the structural, adsorptive, and catalytic properties of Raney nickel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mikhailenko, S.D.; Khodareva, T.A.; Leongardt, E.V.

The effect on Raney nickel catalyst of annealing in hydrogen, and of mild oxidation and subsequent reduction have been studied. The properties investigated are the structure, hydrogen adsorption, and activity for nitrobenzene and potassium maleate liquid-phase hydrogenation. Characterization involved X-ray line broadening, adsorption, and capillary condensation of Ar, XPS, and thermoprogrammed reduction. Thermodesorption studies indicate two forms of adsorbed hydrogen, one of which is a weakly bound molecular form and does not depend on treatment, while the other is strongly bound atomic hydrogen whose amount decreases with increase in the annealing temperature. Annealing hydrogen at T [ge] 200[degrees]C in hydrogen,more » after which the activity for hydrogenation is on par with that of newly prepared catalyst. 33 refs., 10 figs., 5 tabs.« less

Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions

DOE PAGES

Nijem, Nour; Fürsich, Katrin; Bluhm, Hendrik; ...

2015-10-09

Ammonia interactions and competition with water at the interface of nanoporous metal organic framework thin films of HKUST-1 (Cu 3Btc 2 , Btc = 1,3,5-benzenedicarboxylate) are investigated with ambient pressure X-ray photoelectron spectroscopy (APXPS). In the absence of water, ammonia adsorption at the Cu 2+ metal center weakens the metal-linker bond of the framework. In the presence of water, due to the higher binding energy (adsorption strength) of ammonia compared to water, ammonia replaces water at the unsaturated Cu 2+ metal centers. The water molecules remaining in the pores are stabilized by hydrogen bonding to ammonia. Hydrogen bonding between themore » water and ammonia strengthens the metal-ammonia interaction due to cooperative interactions. Cooperative interactions result in a reduction in the metal center oxidation state facilitating linker replacement by other species explaining the previously reported structure degradation.« less

Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nijem, Nour; Fürsich, Katrin; Bluhm, Hendrik

Ammonia interactions and competition with water at the interface of nanoporous metal organic framework thin films of HKUST-1 (Cu 3Btc 2 , Btc = 1,3,5-benzenedicarboxylate) are investigated with ambient pressure X-ray photoelectron spectroscopy (APXPS). In the absence of water, ammonia adsorption at the Cu 2+ metal center weakens the metal-linker bond of the framework. In the presence of water, due to the higher binding energy (adsorption strength) of ammonia compared to water, ammonia replaces water at the unsaturated Cu 2+ metal centers. The water molecules remaining in the pores are stabilized by hydrogen bonding to ammonia. Hydrogen bonding between themore » water and ammonia strengthens the metal-ammonia interaction due to cooperative interactions. Cooperative interactions result in a reduction in the metal center oxidation state facilitating linker replacement by other species explaining the previously reported structure degradation.« less

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Adsorption of ammonia at GaN(0001) surface in the mixed ammonia/hydrogen ambient - a summary of ab initio data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kempisty, Paweł; Krukowski, Stanisław; Interdisciplinary Centre for Materials Modelling, Warsaw University, Pawińskiego 5a, 02-106 Warsaw

Adsorption of ammonia at NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was divided into zones of differently pinned Fermi level: at the Ga broken bond state for dominantly bare surface (region I), at the valence band maximum (VBM) for NH{sub 2} and H-covered surface (region II), and at the conduction band minimum (CBM) for NH{sub 3}-covered surface (region III). The electron counting rule (ECR) extension was formulated for the case of adsorbed molecules. The extensive ab intio calculations show the validity of themore » ECR in case of all mixed H-NH{sub 2}-NH{sub 3} coverages for the determination of the borders between the three regions. The adsorption was analyzed using the recently identified dependence of the adsorption energy on the charge transfer at the surface. For region I ammonia adsorbs dissociatively, disintegrating into a H adatom and a HN{sub 2} radical for a large fraction of vacant sites, while for region II adsorption of ammonia is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. Adsorption of Ammonia in region III (Fermi level pinned at CBM) leads to an unstable configuration both molecular and dissociative, which is explained by the fact that broken Ga-bonds are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating the transfer of these two electrons from the Ga broken bond state to the Fermi level. This is an energetically costly process. Adsorption of ammonia at H-covered site leads to the creation of a NH{sub 2} radical at the surface and escape of H{sub 2} molecule. The process energy is close to 0.12 eV, thus not large, but the direct

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2017-08-18

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

Hydrogen isotope ratios of terrestrial leaf wax n-alkanes from the Tibetan Plateau: Controls on apparent enrichment factors, effect of vapor sources and implication for altimetry

NASA Astrophysics Data System (ADS)

Zhang, Xiaolong; Xu, Baiqing; Günther, Franziska; Mügler, Ines; Lange, Markus; Zhao, Huabiao; Li, Jiule; Gleixner, Gerd

2017-08-01

Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large

Investigating the Influence of Vegetation Type on Modern Leaf Wax Hydrogen Isotopes from a High Latitude Ombrotrophic Bog to Inform Paleoclimate Interpretation

NASA Astrophysics Data System (ADS)

Balascio, N.; D'Andrea, W. J.; Anderson, R. S.

2016-12-01

Leaf wax hydrogen isotopes have been used to track changes in the isotopic composition of meteoric waters in a variety of locations. However, leaf wax compounds preserved in sedimentary environments reflect a mix of plant sources that can have a large range of molecular distributions and biosynthetic fractionation factors potentially complicating paleoclimate interpretations. Here we attempt to constrain the influence of vegetation type on leaf wax hydrogen isotope values at an ombrotrophic bog in northern Norway. We present: (i) δD values of n-alkanes from modern bog vegetation to establish the influence of vegetation type on n-alkane distributions and to provide a site-specific assessment of the biosynthetic isotopic fractionation, and (ii) δD values of n-alkanes from a sediment core spanning the last 10 ka where vegetation changes have been reconstructed based on pollen analysis. We found 14 different vegetation types growing on the bog surface that have average chain lengths from 25 to 30.5 and δD values of n-C25 to n-C33 ranging from -197‰ to -116‰. These samples also have a range of δD values among n-alkane homologues, from 1‰ to 33‰. Based on isotopic measurements of modern bog water, we calculate the average apparent fractionation of n-alkanes to be -108 ± 22‰. Sedimentary δD values of n-C25 to n-C33 over the last 10 ka range from -229 to -158‰ with distinct trends among mid- and long-chain length homologues. Changes in chain lengths and δD values, at times, correspond to vegetation shifts documented by pollen data, but also show unique trends that we interpret to represent variations in local precipitation isotopes related to past hydroclimate change.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Water-Stable Metal-Organic Framework with Three Hydrogen-Bond Acceptors: Versatile Theoretical and Experimental Insights into Adsorption Ability and Thermo-Hydrolytic Stability.

PubMed

Roztocki, Kornel; Lupa, Magdalena; Sławek, Andrzej; Makowski, Wacław; Senkovska, Irena; Kaskel, Stefan; Matoga, Dariusz

2018-03-19

A new microporous cadmium metal-organic framework was synthesized both mechanochemically and in solution by using a sulfonyl-functionalized dicarboxylate linker and an acylhydrazone colinker. The three-dimensional framework is highly stable upon heating to 300 °C as well as in aqueous solutions at elevated temperatures or acidic conditions. The thermally activated material exhibits steep water vapor uptake at low relative pressures at 298 K and excellent recyclability up to 260 °C as confirmed by both quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) method as well as adsorption isotherm measurements. Reversible isotherms and hysteretic isobars recorded for the desorption-adsorption cycles indicate the maximum uptake of 0.19 g/g (at 298 K, up to p/p 0 = 1) or 0.18 g/g (at 1 bar, within 295-375 K range), respectively. The experimental isosteric heat of adsorption (48.9 kJ/mol) indicates noncoordinative interactions of water molecules with the framework. Exchange of the solvent molecules in the as-made material with water, performed in the single-crystal to single-crystal manner, allows direct comparison of both X-ray crystal structures. The single-crystal X-ray diffraction for the water-loaded framework demonstrates the orientation of water clusters in the framework cavities and reveals their strong hydrogen bonding with sulfonyl, acyl, and carboxylate groups of the two linkers. The grand canonical Monte Carlo (GCMC) simulations of H 2 O adsorption corroborate the experimental findings and reveal preferable locations of guest molecules in the framework voids at various pressures. Additionally, both experimental and GCMC simulation insights into the adsorption of CO 2 (at 195 K) on the activated framework are presented.

Selective Hydrogen Isotope Separation via Breathing Transition in MIL-53(Al).

PubMed

Kim, Jin Yeong; Zhang, Linda; Balderas-Xicohténcatl, Rafael; Park, Jaewoo; Hirscher, Michael; Moon, Hoi Ri; Oh, Hyunchul

2017-12-13

Breathing of MIL-53(Al), a flexible metal-organic framework (MOF), leads to dynamic changes as narrow pore (np) transitions to large pore (lp). During the flexible and reversible transition, the pore apertures are continuously adjusted, thus providing the tremendous opportunity to separate mixtures of similar-sized and similar-shaped molecules that require precise pore tuning. Herein, for the first time, we report a strategy for effectively separating hydrogen isotopes through the dynamic pore change during the breathing of MIL-53(Al), a representative of flexible MOFs. The experiment shows that the selectivity for D 2 over H 2 is strongly related to the state of the pore structure of MIL-53(Al). The highest selectivity (S D 2 /H 2 = 13.6 at 40 K) was obtained by optimizing the exposure temperature, pressure, and time to systematically tune the pore state of MIL-53(Al).

Carbon hybridized halloysite nanotubes for high-performance hydrogen storage capacities

PubMed Central

Jin, Jiao; Fu, Liangjie; Yang, Huaming; Ouyang, Jing

2015-01-01

Hybrid nanotubes of carbon and halloysite nanotubes (HNTs) with different carbon:HNTs ratio were hydrothermally synthesized from natural halloysite and sucrose. The samples display uniformly cylindrical hollow tubular structure with different morphologies. These hybrid nanotubes were concluded to be promising medium for physisorption-based hydrogen storage. The hydrogen adsorption capacity of pristine HNTs was 0.35% at 2.65 MPa and 298 K, while that of carbon coated HNTs with the pre-set carbon:HNTs ratio of 3:1 (3C-HNTs) was 0.48% under the same condition. This carbon coated method could offer a new pattern for increasing the hydrogen adsorption capacity. It was also possible to enhance the hydrogen adsorption capacity through the spillover mechanism by incorporating palladium (Pd) in the samples of HNTs (Pd-HNTs) and 3C-HNTs (Pd-3C-HNTs and 3C-Pd-HNTs are the samples with different location of Pd nanoparticles). The hydrogen adsorption capacity of the Pd-HNTs was 0.50% at 2.65 MPa and 298 K, while those of Pd-3C-HNTs and 3C-Pd-HNTs were 0.58% and 0.63%, respectively. In particular, for this spillover mechanism of Pd-carbon-HNTs ternary system, the bidirectional transmission of atomic and molecular hydrogen (3C-Pd-HNTs) was concluded to be more effective than the unidirectional transmission (Pd-3C-HNTs) in this work for the first time. PMID:26201827

Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) α-quartz surface

NASA Astrophysics Data System (ADS)

Abbasi, A.; Nadimi, E.; Plänitz, P.; Radehaus, C.

2009-08-01

In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl-hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.

Effects of shock and Martian alteration on Tissint hydrogen isotope ratios and water content

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Huss, G. R.; Nagashima, K.; Taylor, G. J.; Stöffler, D.; Smith, C. L.; Lee, M. R.

2017-03-01

The Tissint meteorite, a picritic shergottite, fell to Earth in Morocco on the 18th of July 2011, and is only the fifth Martian meteorite witnessed to fall. Hydrogen isotope ratios and water contents are variable within different minerals in Tissint. Ringwoodite and shock melt pockets contain elevated D/H ratios relative to terrestrial values (δD = 761-4224‰). These high ratios in recrystallized phases indicate significant implantation of hydrogen from the D-rich Martian atmosphere during shock. In contrast, although olivine has detectable water abundances (230-485 ppm), it exhibits much lower D/H ratios (δD = +88 to -150‰), suggesting this water was not implanted from the Martian atmosphere. The minimal terrestrial weathering experienced by Tissint gives confidence that the olivine-hosted water has a Martian origin, but its high concentration indicates direct inheritance from the parental melt is improbable, especially given the low pressure of olivine crystallisation. Incorporation of a low δD crustal fluid, or deuteric alteration during crystallisation, could explain the relatively high water contents and low D/H ratios in Tissint olivine.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

PubMed

Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B; Brand, Willi A; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A J; Sauer, Peter E; Sessions, Alex L; Werner, Roland A

2016-04-19

An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.8 to +397.0 mUr or ‰, for δ(13)C(VPDB-LSVEC) from -40.81 to +0.49 mUr and for δ(15)N(Air) from -5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a (2)H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ(2)H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Computational investigation of hydrogen storage on B5V3

NASA Astrophysics Data System (ADS)

Guo, Chen; Wang, Chong

2018-05-01

Based on density functional theory method with 6-311+G(d,p) basis set, the structures, stability and hydrogen storage capacity of B5V3 have been theoretically investigated. It is found that a maximum of seven hydrogen molecules can be adsorbed on B5V3 with gravimetric uptake capacity of 6.39 wt%. The uptake capacity exceeds the target set by the US Department of Energy for vehicular application. Moreover, the average adsorption energy of B5V3 01 (7H2) is 0.60 eV/H2 in the desirable range of reversible hydrogen storage. The kinetic stability of H2 adsorbed on B5V3 01 is confirmed by using gap between highest occupied molecular orbital (HOMO)and the lowest unoccupied molecular orbital (LUMO). The gap value of B5V3 01 (7H2) is 2.81 eV, which indicates the compound with high stability. In addition, the thermochemistry calculation (Gibbs free energy corrected adsorption energy) is used to analyse if the adsorption is favourable or not at different temperatures. It can be found that the Gibbs corrected adsorption energy of B5V3 01 (7H2) is still positive at 400 K at 1 atm. It means that the adsorption of seven hydrogen molecules on B5V3 01 is energetically favourable in a fairly wide temperature range. All the results show that B5V3 01 can be considered as a promising material for hydrogen storage.

Hydrogen molecules and hydrogen-related defects in crystalline silicon

NASA Astrophysics Data System (ADS)

Fukata, N.; Sasaki, S.; Murakami, K.; Ishioka, K.; Nakamura, K. G.; Kitajima, M.; Fujimura, S.; Kikuchi, J.; Haneda, H.

1997-09-01

We have found that hydrogen exists in molecular form in crystalline silicon treated with hydrogen atoms in the downstream of a hydrogen plasma. The vibrational Raman line of hydrogen molecules is observed at 4158 cm-1 for silicon samples hydrogenated between 180 and 500 °C. The assignment of the Raman line is confirmed by its isotope shift to 2990 cm-1 for silicon treated with deuterium atoms. The Raman intensity has a maximum for hydrogenation at 400 °C. The vibrational Raman line of the hydrogen molecules is broad and asymmetric. It consists of at least two components, possibly arising from hydrogen molecules in different occupation sites in crystalline silicon. The rotational Raman line of hydrogen molecules is observed at 590 cm-1. The Raman band of Si-H stretching is observed for hydrogenation temperatures between 100 and 500 °C and the intensity has a maximum for hydrogenation at 250 °C.

Organic silicon compounds anf hydrogen sulfide removal from biogas by mineral and adsorbent

NASA Astrophysics Data System (ADS)

Choi, J.

2015-12-01

Biogas utilized for energy production needs to be free from organic silicon compounds and hydrogen sulfide , as their burning has damaging effects on utilities and humans; organic silicon compounds and hydrogen sulfide can be found in biogas produced from biomass wastes, due to their massive industrial use in synthetic product,such as cosmetics, detergents and paints.Siloxanes and hydrogen sulfide removal from biogas can be carried out by various methods (Ajhar et al., 2010); aim of the present work is to find a single practical andeconomic way to drastically and simultaneously reduce both hydrogen sulfide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleoneet al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing both hydrogen sulphide and volatile siloxane (Decamethycyclopentasiloxane or D5) in a nitrogen stream,typically 25-300 ppm D5 over N2, through an clay minerals, Fe oxides and Silica; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best silica shows an adsorption capacity of 0.2 g D5 per gram of silica. The next thermo gravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on D5 and hydrogen sulphide concentrations. A regenerative silica process is then carried out byheating the silica bed up to 200 ° C and flushing out the adsorbed D5 and hydrogen sulphide samples in a nitrogen stream in athree step heating procedure up to 200 ° C. The adsorption capacity is observed to degrade after cyclingthe samples through several adsorption-desorption cycles.

Adsorption of organic chemicals in soils.

PubMed Central

Calvet, R

1989-01-01

This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

Interaction of Hydrogen with MOF-5.

PubMed

Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

2005-10-06

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.

A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

NASA Astrophysics Data System (ADS)

Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

2018-05-01

The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

Hydrogen isotope fractionation in leaf waxes in the Alaskan Arctic tundra

NASA Astrophysics Data System (ADS)

Daniels, William C.; Russell, James M.; Giblin, Anne E.; Welker, Jeffrey M.; Klein, Eric S.; Huang, Yongsong

2017-09-01

Leaf wax hydrogen isotopes (δDwax) are increasingly utilized in terrestrial paleoclimate research. Applications of this proxy must be grounded by studies of the modern controls on δDwax, including the ecophysiological controls on isotope fractionation at both the plant and landscape scales. Several calibration studies suggest a considerably smaller apparent fractionation between source water and waxes (εapp) at high latitudes relative to temperate or tropical locations, with major implications for paleoclimatic interpretations of sedimentary δDwax. Here we investigate apparent fractionation in the Arctic by tracing the isotopic composition of leaf waxes from production in modern plants to deposition in lake sediments using isotopic observations of precipitation, soil and plant waters, living leaf waxes, and waxes in sediment traps in the Brooks Range foothills of northern Alaska. We also analyze a lake surface sediment transect to compare present-day vegetation assemblages to εapp at the watershed scale. Source water and εapp were determined for live specimens of Eriophorum vaginatum (cottongrass) and Betula nana (dwarf birch), two dominant tundra plants in the Brooks Range foothills. The δD of these plants' xylem water closely tracks that of surface soil water, and reflects a summer-biased precipitation source. Leaf water is enriched by 23 ± 15‰ relative to xylem water for E. vaginatum and by 41 ± 19‰ for B. nana. Evapotranspiration modeling indicates that this leaf water enrichment is consistent with the evaporative enrichment expected under the climate conditions of northern Alaska, and that 24-h photosynthesis does not cause excessive leaf water isotope enrichment. The εapp determined for our study species average -89 ± 14‰ and -106 ± 16‰ for B. nana n-alkanes and n-acids, respectively, and -182 ± 10‰ and -154 ± 26‰ for E. vaginatum n-alkanes and n-acids, which are similar to the εapp of related species in temperate and tropical

Enhanced Hydrogen Dipole Physisorption, Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Channing

2014-01-03

The hydrogen gas adsorption effort at Caltech was designed to probe and apply our understanding of known interactions between molecular hydrogen and adsorbent surfaces as part of a materials development effort to enable room temperature storage of hydrogen at nominal pressure. The work we have performed over the past five years has been tailored to address the outstanding issues associated with weak hydrogen sorbent interactions in order to find an adequate solution for storage tank technology.

Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

NASA Astrophysics Data System (ADS)

Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

2015-12-01

In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

A new combined nanoSIMS and continuous-flow IRMS approach to measure hydrogen isotopes from water in hydrated rhyolitic glass

NASA Astrophysics Data System (ADS)

Gatti, E.; Kitchen, N.; Newman, S.; Guan, Y.; Westgate, J.; Pearce, N. J. G.; Nikolic, D.; Eiler, J. M.

2016-12-01

The hydrogen-isotope value of water of hydration (or secondary water) preserved in rhyolitic glasses may provide significant insights regarding the climate at the time of their deposition and the impact of super-eruptions upon the environment. However, the ability of the glass to retain the environmental D/H isotopic signal after hydration needs to be tested, since modifications to the D/H systematics may result from the continuous exchange of D/H with the atmosphere or condensed water after initial glass hydration. Ideal geological archives to test whether the glass retains its original hydrogen signal are sediments in natural waters and ice cores, which preserve tephra in constrained horizons that can be independently isotopically characterised. However, tephra in marine and fresh water sediments and ice cores are often present in concentrations of the order of 1000 grains/cm3 (<5 mg of collectible material). Traditional IRMS methods require much more material ( 100-500 mg) and therefore cannot be applied. We present here a new integrated nanoSIMS and continuous flow IRMS approach to understand how water is distributed within single glass grains (diffusion profiles), quantify the time of hydration of young (Holocene) and old (Miocene) already well-characterised rhyolitic glasses, and measure the D/H ratio of the hydration water on single grains and bulk material consisting of only approximately 0.1-1 mg. The IRMS method measures the absolute abundance of hydrogen released from the sample by continuous-flow mass spectrometry. Current data indicates that the method can accurately measure a hydrogen signal from a rock sample containing at least 400 nanomoles of H2, corresponding to 70 µg of water, which translates to 1 mg of hydrous glass (>3 wt%) or 15 mg of dry ( 0.5 wt%) obsidian chips. The method can be improved by reducing the blank to <1 nmol/min and reducing capillary empty space. The bulk results obtained with the continuous-flow IRMS method will be

Large entropy derived from low-frequency vibrations and its implications for hydrogen storage

NASA Astrophysics Data System (ADS)

Wang, Xiaoxia; Chen, Hongshan

2018-02-01

Adsorption and desorption are driven by the energy and entropy competition, but the entropy effect is often ignored in hydrogen storage and the optimal adsorption strength for the ambient storage is controversial in the literature. This letter investigated the adsorption states of the H2 molecule on M-B12C6N6 (M = Li, Na, Mg, Ca, and Sc) and analyzed the correlation among the zero point energy (ZPE), the entropy change, and the adsorption energy and their effects on the delivery capacities. The ZPE has large correction to the adsorption energy due to the light mass of hydrogen. The computations show that the potential energies along the spherical surface centered at the alkali metals are very flat and it leads to large entropy (˜70 J/mol.K) of the adsorbed H2 molecules. The entropy change can compensate the enthalpy change effectively, and the ambient storage can be realized with relatively weak adsorption of ΔH = -12 kJ/mol. The results are encouraging and instructive for the design of hydrogen storage materials.

Mass dependence of calcium isotope fractionations in crown-ether resin chromatography.

PubMed

Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Tositaka; Sakuma, Yoichi; Suzuki, Tatsuya; Umehara, Saori; Kishimoto, Tadahumi

2010-06-01

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60micro Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of (42)Ca, (43)Ca, (44)Ca, and (48)Ca against (40)Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient epsilon is 3.1x10(-3) for the pair of (40)Ca and (48)Ca. Productivity of enriched (48)Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate.

A first-principles study of hydrogen storage capacity based on Li-Na-decorated silicene.

PubMed

Sheng, Zhe; Wu, Shujing; Dai, Xianying; Zhao, Tianlong; Hao, Yue

2018-05-23

Surface decoration with alkali metal adatoms has been predicted to be promising for silicene to obtain high hydrogen storage capacity. Herein, we performed a detailed study of the hydrogen storage properties of Li and Na co-decorated silicene (Li-Na-decorated silicene) based on first-principles calculations using van der Waals correction. The hydrogen adsorption behaviors, including the adsorption order, the maximum capacity, and the corresponding mechanism were analyzed in detail. Our calculations show that up to three hydrogen molecules can firmly bind to each Li atom and six for each Na atom, respectively. The hydrogen storage capacity is estimated to be as high as 6.65 wt% with a desirable average adsorption energy of 0.29 eV/H2. It is confirmed that both the charge-induced electrostatic interaction and the orbital hybridizations play a great role in hydrogen storage. Our results may enhance our fundamental understanding of the hydrogen storage mechanism, which is of great importance for the practical application of Li-Na-decorated silicene in hydrogen storage.

A relativistic density functional study of the role of 5f electrons in atomic and molecular adsorptions on actinide surfaces

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul

Atomic and molecular adsorptions of oxygen and hydrogen on actinide surfaces have been studied within the generalized gradient approximations to density functional theory (GGA-DFT). The primary goal of this work is to understand the details of the adsorption processes, such as chemisorption sites, energies, adsorption configurations and activation energies for dissociation of molecules; and the signature role of the plutonium 5f electrons. The localization of the 5f electrons remains one of central questions in actinides and one objective here is to understand the extent to which localizations plays a role in adsorption on actinide surfaces. We also investigated the magnetism of the plutonium surfaces, given the fact that magnetism in bulk plutonium is a highly controversial issue, and the surface magnetism of it is not a well explored territory. Both the non-spin-polarized and spin-polarized calculations have been performed to arrive at our conclusions. We have studied both the atomic and molecular hydrogen and oxygen adsorptions on plutonium (100) and (111) surfaces. We have also investigated the oxygen molecule adsorptions on uranium (100) surface. Comparing the adsorption on uranium and plutonium (100) surfaces, we have seen that O2 chemisorption energy for the most favorable adsorption site on uranium surface has higher chemisorption energy, 9.492 eV, than the corresponding plutonium site, 8.787 eV. Also degree of localization of 5f electrons is less for uranium surface. In almost all of the cases, the most favorable adsorption sites are found where the coordination numbers are higher. For example, we found center sites are the most favorable sites for atomic adsorptions. In general oxygen reacts more strongly with plutonium surface than hydrogen. We found that atomic oxygen adsorption energy on (100) surface is 3.613 eV more than that of the hydrogen adsorptions, considering only the most favorable site. This is also true for molecular adsorptions, as the

Possible selective adsorption of enantiomers by Na-montmorillonite

NASA Technical Reports Server (NTRS)

Friebele, E.; Shimoyama, A.; Ponnamperuma, C.

1981-01-01

Racemic amino acids including (D,L) alpha-alamine, (D,L) alpha-aminobutyric acid, (D,L) valine, and (D,L) norvaline were incubated with Na-montmorillonite at 100% CEC at three hydrogen ion concentrations, and amino acid adsorption was determined by ion exchange chromatography. Enantiomers were analyzed by gas chromatography. Differences in the quantities of D and L enantiomers in any of the fractions was no larger than a few percent. Although a large difference in the adsorption of the amino acid enantiomers was not observed, the analysis may indicate a small preferential adsorption (0.5-2%) of L-amino acids by Na-montmorillonite.

Approaches to Plant Hydrogen and Oxygen Isoscapes Generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

West, Jason B.; Kreuzer-Martin, Helen W.; Ehleringer, James

2009-12-01

Plant hydrogen and oxygen isoscapes have been utilized to address important and somewhat disparate research goals. The isotopic composition of leaf water affects the isotopic composition of atmospheric CO2 and O2 and is a logical starting point for understanding the isotopic composition of plant organic compounds since photosynthesis occurs in the leaf water environment. Leaf water isoscapes have been produced largely as part of efforts to understand atmospheric gas isotopic composition. The isotopic composition of plant organic matter has also been targeted for its potential to serve as a proxy for past environmental conditions. Spatially distributed sampling and modeling ofmore » modern plant H & O isoscapes can improve our understanding of the controls of the isotope ratios of compounds such as cellulose or n-alkanes from plants and therefore their utility for paleoreconstructions. Spatially varying plant hydrogen and oxygen isotopes have promise for yielding geographic origin information for a variety of plant products, including objects of criminal forensic interest or food products. The future has rich opportunities for the continued development of mechanistic models, methodologies for the generation of hydrogen and oxygen isoscapes, and cross-disciplinary interactions as these tools for understanding are developed, shared, and utilized to answer large-scale questions.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Copper(II) adsorption on the kaolinite(001) surface: Insights from first-principles calculations and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kong, Xiang-Ping; Wang, Juan

2016-12-01

The adsorption behavior of Cu(II) on the basal hydroxylated kaolinite(001) surface in aqueous environment was investigated by first-principles calculations and molecular dynamics simulations. Structures of possible monodentate and bidentate inner-sphere adsorption complexes of Cu(II) were examined, and the charge transfer and bonding mechanism were analyzed. Combining the binding energy of complex, the radial distribution function of Cu(II) with oxygen and the extended X-ray absorption fine structure data, monodentate complex on site of surface oxygen with ;upright; hydrogen and bidentate complex on site of two oxygens (one with ;upright; hydrogen and one with ;lying; hydrogen) of single Al center have been found to be the major adsorption species of Cu(II). Both adsorption species are four-coordinated with a square planar geometry. The distribution of surface hydroxyls with ;lying; hydrogen around Cu(II) plays a key role in the structure and stability of adsorption complex. Upon the Mulliken population analysis and partial density of states, charge transfer occurs with Cu(II) accepting some electrons from both surface oxygens and aqua oxygens, and the bonding Cu 3d-O 2p state filling is primarily responsible for the strong covalent interaction of Cu(II) with surface oxygen.

Regenerable Nickel-Functionalized Activated Carbon Cathodes Enhanced by Metal Adsorption to Improve Hydrogen Production in Microbial Electrolysis Cells.

PubMed

Kim, Kyoung-Yeol; Yang, Wulin; Logan, Bruce E

2018-06-07

While nickel is a good alternative to platinum as a catalyst for the hydrogen evolution reaction, it is desirable to reduce the amount of nickel needed for cathodes in microbial electrolysis cells (MECs). Activated carbon (AC) was investigated as a cathode base structure for Ni as it is inexpensive and an excellent adsorbent for Ni, and it has a high specific surface area. AC nickel-functionalized electrodes (AC-Ni) were prepared by incorporating Ni salts into AC by adsorption, followed by cathode fabrication using a phase inversion process using a poly(vinylidene fluoride) (PVDF) binder. The AC-Ni cathodes had significantly higher (∼50%) hydrogen production rates than controls (plain AC) in smaller MECs (static flow conditions) over 30 days of operation, with no performance decrease over time. In larger MECs with catholyte recirculation, the AC-Ni cathode produced a slightly higher hydrogen production rate (1.1 ± 0.1 L-H 2 /L reactor /day) than MECs with Ni foam (1.0 ± 0.1 L-H 2 /L reactor /day). Ni dissolution tests showed that negligible amounts of Ni were lost into the electrolyte at pHs of 7 or 12, and the catalytic activity was restored by simple readsorption using a Ni salt solution when Ni was partially removed by an acid wash.

Adsorption-oxidation of hydrogen sulfide on Fe/walnut-shell activated carbon surface modified by NH3-plasma.

PubMed

Ning, Ping; Liu, Sijian; Wang, Chi; Li, Kai; Sun, Xin; Tang, Lihong; Liu, Gui

2018-02-01

Walnut-shell activated carbon (WSAC) supported ferric oxide was modified by non-thermal plasma (NTP), and the removal efficiency for hydrogen sulfide over Fe/WSAC modified by dielectric barrier discharge (DBD) was significantly promoted. The sample modified for 10min and 6.8kV output (30V input voltage) maintained 100% H 2 S conversion over a long reaction time of 390min. The surface properties of adsorbents modified by NTP under different conditions were evaluated by the methods of X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) analysis and in-situ Fourier transform infrared spectroscopy (FTIR), to help understand the effect of the NTP treatment. NTP treatment enhanced the adsorption capacity of Fe/WSAC, which could due to the formation of micro-pores with sizes of 0.4, 0.5 and 0.75nm. XPS revealed that chemisorbed oxygen changed into lattice oxygen after NTP treatment, and lattice oxygen is beneficial for H 2 S oxidation. From the in-situ FTIR result, transformation of the reaction path on Fe/WSAC was observed after NTP modification. The research results indicate that NTP is an effective method to improve the surface properties of the Fe/WSAC catalyst for H 2 S adsorption-oxidation. Copyright © 2017. Published by Elsevier B.V.

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

Fibrinogen adsorption on blocked surface of albumin.

PubMed

Holmberg, Maria; Hou, Xiaolin

2011-05-01

We have investigated the adsorption of albumin and fibrinogen onto PET (polyethylene terephthalate) and glass surfaces and how pre-adsorption of albumin onto these surfaces can affect the adsorption of later added fibrinogen. For materials and devices being exposed to blood, adsorption of fibrinogen is often a non-wanted event, since fibrinogen is part of the clotting cascade and unspecific adsorption of fibrinogen can have an influence on the activation of platelets. Albumin is often used as blocking agent for avoiding unspecific protein adsorption onto surfaces in devices designed to handle biological samples, including protein solutions. It is based on the assumption that proteins adsorbs as a monolayer on surfaces and that proteins do not adsorb on top of each other. By labelling albumin and fibrinogen with two different radioactive iodine isotopes that emit gamma radiation with different energies, the adsorption of both albumin and fibrinogen has been monitored simultaneously on the same sample. Information about topography and coverage of adsorbed protein layers has been obtained using AFM (Atomic Force Microscopy) analysis in liquid. Our studies show that albumin adsorbs in a multilayer fashion on PET and that fibrinogen adsorbs on top of albumin when albumin is pre-adsorbed on the surfaces. Copyright © 2010 Elsevier B.V. All rights reserved.