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Sample records for hydrogen isotope anomalies

  1. 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.

  2. 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

  3. 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

  4. Physicochemical isotope anomalies

    SciTech Connect

    Esat, T.M.

    1988-06-01

    Isotopic composition of refractory elements can be modified, by physical processes such as distillation and sputtering, in unexpected patterns. Distillation enriches the heavy isotopes in the residue and the light isotopes in the vapor. However, current models appear to be inadequate to describe the detailed mass dependence, in particular for large fractionations. Coarse- and fine-grained inclusions from the Allende meteorite exhibit correlated isotope effects in Mg both as mass-dependent fractionation and residual anomalies. This isotope pattern can be duplicated by high temperature distillation in the laboratory. A ubiquitous property of meteoritic inclusions for Mg as well as for most of the other elements, where measurements exist, is mass-dependent fractionation. In contrast, terrestrial materials such as microtektites, tektite buttons as well as lunar orange and green glass spheres have normal Mg isotopic composition. A subset of interplanetary dust particles labelled as chondritic aggregates exhibit excesses in {sup 26}Mg and deuterium anomalies. Sputtering is expected to be a dominant mechanism in the destruction of grains within interstellar dust clouds. An active proto-sun as well as the present solar-wind and solar-flare flux are of sufficient intensity to sputter significant amounts of material. Laboratory experiments in Mg show widespread isotope effects including residual {sup 26}Mg excesses and mass dependent fractionation. It is possible that the {sup 26}Mg excesses in interplanetary dust is related to sputtering by energetic solar-wind particles. The implication if the laboratory distillation and sputtering effects are discussed and contrasted with the anomalies in meteoritic inclusions the other extraterrestrial materials the authors have access to.

  5. Isotopic anomalies in extraterrestrial grains.

    PubMed

    Ireland, T R

    1996-03-01

    Isotopic compositions are referred to as anomalous if the isotopic ratios measured cannot be related to the terrestrial (solar) composition of a given element. While small effects close to the resolution of mass spectrometric techniques can have ambiguous origins, the discovery of large isotopic anomalies in inclusions and grains from primitive meteorites suggests that material from distinct sites of stellar nucleosynthesis has been preserved. Refractory inclusions, which are predominantly composed of the refractory oxides of Al, Ca, Ti, and Mg, in chondritic meteorites commonly have excesses in the heaviest isotopes of Ca, Ti, and Cr which are inferred to have been produced in a supernova. Refractory inclusions also contain excess 26Mg from short lived 26Al decay. However, despite the isotopic anomalies indicating the preservation of distinct nucleosynthetic sites, refractory inclusions have been processed in the solar system and are not interstellar grains. Carbon (graphite and diamond) and silicon carbide grains from the same meteorites also have large isotopic anomalies but these phases are not stable in the oxidized solar nebula which suggests that they are presolar and formed in the circumstellar atmospheres of carbon-rich stars. Diamond has a characteristic signature enriched in the lightest and heaviest isotopes of Xe, and graphite shows a wide range in C isotopic compositions. SiC commonly has C and N isotopic signatures which are characteristic of H-burning in the C-N-O cycle in low-mass stars. Heavier elements such as Si, Ti, Xe, Ba, and Nd, carry an isotopic signature of the s-process. A minor population of SiC (known as Grains X, ca. 1%) are distinct in having decay products of short lived isotopes 26Al (now 26Mg), 44Ti (now 44Ca), and 49V (now 49Ti), as well as 28Si excesses which are characteristic of supernova nucleosynthesis. The preservation of these isotopic anomalies allows the examination of detailed nucleosynthetic pathways in stars. PMID

  6. Titanium isotopic anomalies in meteorites

    NASA Technical Reports Server (NTRS)

    Niemeyer, S.; Lugmair, G. W.

    1984-01-01

    Studies of Ti isotopic compositions have shown that virtually every Ca-Al-rich Allende inclusion contains anomalous Ti. The present investigation is concerned with the results of a study of Ti isotopic compositions in meteorites. One objective of the study is to evaluate the possibility of a relation between oxygen and Ti anomalies, while another objective is to explore questions regarding the origin of the Ti anomalies. A summary of the major experimental findings of the study of Ti isotopic compositions is also presented. It is noted that an assessment of the implications of the Ti results favors a chemical memory type of model in which products from various nucleosynthetic sources survive in mineral grains. Isotopic heterogeneities are then preserved due to incomplete mixing and/or equilibriation with the bulk of solar system matter. Strong arguments are found to exist against a pure late supernova injection model.

  7. Titanium isotopic anomalies in meteorites

    NASA Astrophysics Data System (ADS)

    Neimeyer, S.; Lugmair, G. W.

    1984-07-01

    Studies of Ti isotopic compositions have shown that virtually every Ca-Al-rich Allende inclusion contains anomalous Ti. The present investigation is concerned with the results of a study of Ti isotopic compositions in meteorites. One objective of the study is to evaluate the possibility of a relation between oxygen and Ti anomalies, while another objective is to explore questions regarding the origin of the Ti anomalies. A summary of the major experimental findings of the study of Ti isotopic compositions is also presented. It is noted that an assessment of the implications of the Ti results favors a chemical memory type of model in which products from various nucleosynthetic sources survive in mineral grains. Isotopic heterogeneities are then preserved due to incomplete mixing and/or equilibriation with the bulk of solar system matter. Strong arguments are found to exist against a pure late supernova injection model.

  8. Chromium isotopic anomalies in the Murchison meteorite

    NASA Astrophysics Data System (ADS)

    Esat, T. M.; Ireland, T. R.

    1989-02-01

    The abundances of chromium isotopes, in refractory inclusions from the Allende meteorite, show wide-spread anomalies. The chromium isotope anomalies are similar in pattern to the anomalies discovered in Ca and Ti. The largest effects occur at the neutron-rich isotopes Ca-48, Ti-50 and Cr-54. Individual Cr-rich pink spinels, from the Murchison meteorite, exhibit large and variable excesses in Cr-53 and Cr-54 including the largest Cr-53 anomaly so far reported. Magnesium isotopes, in Murchison Cr-poor blue spinels, also show variable anomalies in Mg-26 including mass-dependent fractionation favoring the lighter isotopes. The Cr-53, Cr-54 and Mg-26 anomalies in Murchison spinels are indicative of a heterogeneous distribution of magnesium and chromium isotopes in the early solar nebula and require a contribution from several nucleosynthetic components in addition to physicochemical processing.

  9. HYDROGEN ISOTOPE TARGETS

    DOEpatents

    Ashley, R.W.

    1958-08-12

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

  10. Zinc Isotope Anomalies in bulk Chondrites

    NASA Astrophysics Data System (ADS)

    Savage, P. S.; Boyet, M.; Moynier, F.

    2014-09-01

    This study is the first to demonstrate that Zn isotope anomalies are present in bulk primitive meteorites, consistent with the injection of material derived from a neutron-rich supernova source into the solar nebula.

  11. Chromium isotopic anomalies in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.

    1986-01-01

    Abundances of the chromium isotopes in terrestrial and bulk meteorite samples are identical to 0.01 percent. However, Ca-Al-rich inclusions from the Allende meteorite show endemic isotopic anomalies in chromium which require at least three nucleosynthetic components. Large anomalies at Cr-54 in a special class of inclusions are correlated with large anomalies at Ca-48 and Ti-50 and provide strong support for a component reflecting neutron-rich nucleosynthesis at nuclear statistical equilibrium. This correlation suggests that materials from very near the core of an exploding massive star may be injected into the interstellar medium.

  12. Isotopic anomalies - Chemical memory of Galactic evolution

    NASA Technical Reports Server (NTRS)

    Clayton, Donald D.

    1988-01-01

    New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC.

  13. 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.

  14. 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.

  15. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

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

  16. 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.

  17. MULTIPLE ORIGINS OF NITROGEN ISOTOPIC ANOMALIES IN METEORITES AND COMETS

    SciTech Connect

    Aleon, Jerome

    2010-10-20

    Isotopic fractionation and mixing calculations compared with coupled hydrogen and nitrogen isotopic composition of organic molecules from primitive chondrites, interplanetary dust particles (IDPs), and comets C/1995 O1 (Hale-Bopp) and 81P/Wild2 reveal that meteoritic and cometary organic matter contains three different isotopic components of different origins. (1) A major component of carbonaceous chondrites, IDPs, and comets Hale-Bopp and Wild2 shows correlated H and N isotopic compositions attributable to isotope exchange between an organic matter of solar composition and a reservoir formed by ion-molecule reactions at T < 25 K under conditions where competing reactions are strongly inhibited, possibly in the final evolutionary stages of the presolar cloud core, or more likely in the coldest outer regions of the solar protoplanetary disk. (2) In carbonaceous chondrites, IDPs, and comet Wild2, this component is mixed with a {sup 15}N-rich component having identical {sup 15}N and D enrichments relative to the protosolar gas. Temperatures > 100 K deduced from the low D/H ratio and an anti-correlation between the abundance of this component and meteoritic age indicate a late origin in the solar protoplanetary disk. N{sub 2} self-shielding and the non-thermal nucleosynthesis of {sup 15}N upon irradiation are possible but unlikely sources of this component, and a chemical origin is preferred. (3) An interstellar component with highly fractionated hydrogen isotopes and unfractionated nitrogen isotopes is present in ordinary chondrites. A dominantly solar origin of D and {sup 15}N excesses in primitive solar system bodies shows that isotopic anomalies do not necessarily fingerprint an interstellar origin and implies that only a very small fraction of volatile interstellar matter survived the events of solar system formation.

  18. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  19. Apparatus and process for separating hydrogen isotopes

    DOEpatents

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

    2013-06-25

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

  20. Wolf-Rayet Stars and the Isotopic Anomaly Connection

    NASA Astrophysics Data System (ADS)

    Arnould, M.; Paulus, G.; Meynet, G.

    1993-07-01

    Isotopic anomalies are now known to be carried by high-temperature inclusions of primitive meteorites that formed from solar reservoirs out of equilibrium with the rest of the solar nebula, as well as by various types of grains (diamond, graphite, SiC) that are considered to be of circumstellar origin, and have survived the process of incorporation into the solar system (see e.g. [1] for a recent review). Such anomalies provide new clues to many important astrophysical problems, and raise the question of their nucleosynthetic origin. In fact, they offer the exciting perspective of confronting abundance observations with nucleosynthesis models for a very limited number of events, even possibly a single one. This situation is in marked contrast with the one encountered when trying to understand the bulk solar system composition. Up to now, Red Giant stars, massive mass loosing objects (of the Wolf-Rayet type), novae or supernovae have been proposed as possible contributors to the observed anomalies. In this paper, we revisit the role that could possibly be played in that respect by Wolf-Rayet (WR) stars. Wolf-Rayet stars are appealing isotopic anomaly contributors for many reasons. In particular (1) they are observed to loose mass at very large rates that can exceed 10^-5M solar masses yr^-l, the ejected material being contaminated with the products of hydrogen and helium burning, and (2) certain WR stars are known to make dust episodically in their winds [e.g., 2]. In addition, the role of WR stars would be well in line with the "bing-bang" model for the isotopic anomalies promoted by Reeves [3]. The aim of this contribution is to extent and update previous calculations [4,5] of the isotopic anomalies that could be carried by the wind of WR stars of various masses and initial compositions during different phases of their evolution, those anomalies possibly loading circumstellar WR grains. The calculation of the WR wind composition is performed on grounds of detailed

  1. The identification of meteorite inclusions with isotope anomalies

    NASA Astrophysics Data System (ADS)

    Papanastassiou, D. A.; Brigham, C. A.

    1989-03-01

    Ca-Al refractory inclusions with characteristic chemical and mineralogical compositions show an enhanced occurrence of 20 pct of isotope anomalies reflecting unknown nucleosynthetic effects for O and Mg. The anomalies are characterized by large isotope fractionation in Mg, apparent deficits in Mg-26/Mg-24, and large correlated effects for isotopes of Ca, Ti, and Cr. These isotope patterns define exotic components depleted in the most neutron-rich isotopes of Ca, Ti, and Cr, or components depleted in isotopes produced in explosive O and Si burning. An opaque assemblage within one of the inclusions yields isotope anomalies in Cr similar to the bulk inclusion and must be intrinsically part of the inclusion and not a trapped, foreign grain aggregate.

  2. Nucleosynthetic strontium isotope anomalies in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Yokoyama, Tetsuya; Fukami, Yusuke; Okui, Wataru; Ito, Nobuaki; Yamazaki, Hiroshi

    2015-04-01

    Precise Sr isotopic compositions in samples from sequential acid leaching experiments have been determined for three carbonaceous chondrites, Allende, Murchison, and Tagish Lake, together with those in the bulk aliquots of these meteorites. The chondritic acid leachates and residues were characterized by Sr isotope anomalies with variable μ84Sr values (106 relative deviation from a standard material) ranging from +120 to - 4700 ppm, documenting multiple nucleosynthetic sources within a single meteorite. In addition, the μ84Sr patterns across leaching samples for individual chondrites differed from one another. The highest μ84Sr values were observed for leaching Step 3 (HCl+H2O, 75 °C) for Allende and Murchison likely because of the incorporation of calcium and aluminum-rich inclusions (CAIs). In contrast, extremely low μ84Sr values were observed in the later fractions (Steps 6 and 7) for Murchison and Tagish Lake, suggesting the existence of s-process-enriched presolar SiC grains derived from AGB stars. A μ84Sr-ɛ54Cr diagram was prepared with the CAIs and bulk aliquots of carbonaceous chondrites and other meteorites (noncarbonaceous) that were plotted separately; however, they still formed a global positive correlation. CAIs presented the highest μ84Sr and ɛ54Cr values, whereas carbonaceous chondrites and noncarbonaceous meteorites had intermediate and the lowest μ84Sr and ɛ54Cr values, respectively. The positive trend was interpreted as resulting from global thermal processing in which sublimation of high μ84Sr and ɛ54Cr carriers generated the excess μ84Sr and ɛ54Cr signatures in CAIs, while noncarbonaceous planetesimals accreted from materials that underwent significant thermal processing and thus had relatively low μ84Sr and ɛ54Cr values. Apart from the global trend, the carbonaceous chondrites and noncarbonaceous meteorites both exhibited intrinsic variations that highlight an isotopic dichotomy similar to that observed in other isotope

  3. Titanium isotopic anomalies in chondrules from carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Niemeyer, S.

    1988-02-01

    Isotopic analyses of Ti from a suite of eight Allende chondrules were conducted to determine whether any relationship exists between the composition and structure of a chondrule and the Ti isotopic patterns. Four of the eight chondrules displayed well-resolved anomalies with respect to Ti-50/Ti-46 ratio, which ranged from a Ti-50 deficit of two epsilon-units to a T-50 excess of nine epsilon-units. No clear link was found between the structure of the chondrules and the Ti anomalies (although the chondrule with by far the largest Ti isotopic anomaly was also Al-rich, suggesting that there might exist a complicated relationship between the degree of refractory enrichment and the magnitude of Ti isotopic anomalies.

  4. Reconstruction of the West Pacific ENSO precipitation anomaly using the compound-specific hydrogen isotopic record of marine lake sediments of Palau

    NASA Astrophysics Data System (ADS)

    Smittenberg, R. H.; Sachs, J. P.; Dawson, M. N.

    2004-12-01

    There is still much uncertainty whether the El Niño Southern Oscillation (ENSO) will become stronger or more frequent in a warming global climate. A principal reason for this uncertainty stems from a glaring lack of paleoclimate data in the equatorial Pacific, which hampers model validation. To partly resolve this data deficiency, sediments of three marine anoxic lakes were cored in Palau, an island group that lies in the heart of the West Pacific Warm Pool. The lakes contain seawater that seeps through fissures in the surrounding karst, and they are permanently stratified due to fresh water input provided by the year-round wet climate (map 1970-2000 = 3.7m). During ENSO events, however, the islands suffer from drought. The surface water hydrogen isotopic compositions in the lakes are sensitive to the relative proportions of D-depleted rainwater and D-enriched seawater, and are therefore sensitive to ENSO events. The lake surface water H/D values are recorded by algal and bacterial biomarkers that are preserved well in the highly organic and anoxic sediments, which accumulate relatively fast (mean 1 mm/yr). Ongoing down core measurement will eventually result in a precipitation proxy record of the islands. To obtain endmember D/H values, a comprehensive set of water samples from sea, lakes and rain water was obtained, as well as suspended particulate matter. Higher plant biomarker D/H values derived from the jungle vegetation surrounding the lakes may render supporting climatic proxy data, being influenced by evapotranspiration. Some lakes are inhabited by millions of jellyfish (Mastigias) that live in symbiosis with zooxanthellae. The jellyfish of one of the investigated lakes disappeared completely after the last large ENSO event in 1998 (returning in 2000-01), and a correlation is suggested. To reconstruct the history of jellyfish occurrence, jellyfish and sedimentary lipids were extracted and compared. In addition to a possible ENSO proxy record, this

  5. 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.

  6. 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.

  7. Some key issues in isotopic anomalies - Astrophysical history and aggregation

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1982-01-01

    Astrophysical history, particularly that period extending from stellar nucleosynthesis events to the formation of meteorites, is discussed as the key element for the understanding of isotopic anomalies in meteorites. The bulk homogeneity of the interstellar medium is considered, and it is argued that, despite the presence of spatial inhomogeneities due to different nucleosynthesis rates in different parts of the galaxy and supernova ejecta, a cosmic chemical memory of nucleosynthesis patterns, rather than an inhomogeneous injection, is the source of isotopic anomalies. According to this view, volatility patterns and some isotopic patterns are mapped onto a grain-size spectrum, and the FUN systematics may be explained by interstellar sputtering. Furthermore, meteoritic He and Ne abundances are inferred to be presolar, and the ubiquitous titanium isotopic anomalies are explained by processes of chemical fixation and condensation in varying environments.

  8. 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.

  9. Barium and neodymium isotopic anomalies in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Mcculloch, M. T.; Wasserburg, G. J.

    1978-01-01

    The discovery of Ba and Nd isotopic anomalies in two inclusions from the Allende meteorite is reported. The inclusions are Ca-Al-rich objects typical of the type considered as high-temperature condensation products in the solar nebula and contain distinctive Mg and O isotopic anomalies of the FUN (mass Fractionation, Unknown Nuclear processes) type. Mass-spectrometry results are discussed which show that inclusion C1 has anomalies in Ba at masses 134 and 136, while inclusion EK1-4-1 exhibits large marked negative anomalies at 130, 132, 134, and 136, as well as a positive anomaly at 137. It is also found that inclusion EK1-4-1 shows marked negative anomalies in Nd at masses 142, 146, 148, and 150, in addition to a positive anomaly at 145. These isotopic shifts are attributed to addition of r-process nuclei rather than mass fractionation. It is suggested that an onion-shell supernova explosion followed by injection into the solar nebula is the most likely generic model that may explain the observations.

  10. Zinc isotope anomalies. [in Allende meteorite

    NASA Technical Reports Server (NTRS)

    Volkening, J.; Papanastassiou, D. A.

    1990-01-01

    The Zn isotope composition in refractory-element-rich inclusions of the Allende meteorite are determined. Typical inclusions contain normal Zn. A unique inclusion of the Allende meteorite shows an excess for Zn-66 of 16.7 + or - 3.7 eu (1 eu = 0.01 percent) and a deficit for Zn-70 of 21 + or - 13 eu. These results indicate the preservation of exotic components even for volatile elements in this inclusion. The observed excess Zn-66 correlates with excesses for the neutron-rich isotopes of Ca-48, Ti-50, Cr-54, and Fe-58 in the same inclusion.

  11. Zinc isotope anomalies in Allende meteorite inclusions

    NASA Technical Reports Server (NTRS)

    Loss, R. D.; Lugmair, G. W.

    1990-01-01

    The isotopic compositions of Zn, Cr, Ti, and Ca have been measured in a number of CAIs from the Allende meteorite. The aim was to test astrophysical models which predict large excesses of Zn-66 to accompany excesses in the neutron-rich isotopes of Ca, Ti, Cr, and Ni. Some of the CAIs show clearly resolved but small excesses for Zn-66 which are at least an order of magnitude smaller than predicted. This result may simply reflect the volatility and chemical behavior of Zn as compared to the other (more refractory) anomalous elements found in these samples. Alternatively, revision of parameters and assumptions used for the model calculations may be required.

  12. 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.

  13. 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).

  14. Endemic Mo Isotopic Anomalies in Iron and Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.; Ngo, H. H.

    2004-01-01

    Mo in refractory interstellar grains shows large isotope anomalies. Recent Mo studies showed isotope effects in Allende and Murchison, and in iron meteorites, mesosiderites, and pallasites. Excesses of p- and r-process isotopes (or depletion of sprocess isotopes) of up to 3.5 epsilon units (epsilon u=parts in 10(exp 4)) were reported. We have reported on endemic isotope anomalies in Ru. Other workers have resolved no isotope anomalies for Mo or Ru and have claimed that the work by others is incorrect. Because Ru isotopes can interfere at Mo-96, Mo-98, Mo-100, we improved the chemical separations and eliminated interferences. For Mo work, we used the same solutions from which we separated and analyzed Ru. Three of the iron meteorites (Coahuila, Cape York, and Cape of Good Hope) were chosen for their large Mo isotopic effects. Mo was loaded on outgassed Re filaments, and then reduced; we used Ba(OH)2-NaOH as emitter, and measured Mo in static mode, as MoO3(-). We used Mo-98/Mo-96 for the mass fractionation correction (exponential law). No interferences from Ru or Zr isotopes were detected using the electron multiplier and no corrections were needed. For results on Mo standards we show 2 sigma(not 2 sigma mean) external precision better than: 0.7 epsilon u for Mo-94/Mo-96 and Mo-95/Mo-96; 1.0 epsilon u for Mo-92/Mo-96 and Mo-97/Mo-96; 1.4 epsilon u for Mo-100/Mo-96. Reproducibility for Mo standards is shown as contours (blue lines).

  15. The longevity of the South Pacific isotopic and thermal anomaly

    USGS Publications Warehouse

    Staudigel, H.; Park, K.-H.; Pringle, M.; Rubenstone, J.L.; Smith, W.H.F.; Zindler, A.

    1991-01-01

    The South Pacific is anomalous in terms of the Sr, Nd, and Pb isotope ratios of its hot spot basalts, a thermally enhanced lithosphere, and possibly a hotter mantle. We have studied the Sr, Nd, and Pb isotope characteristics of 12 Cretaceous seamounts in the Magellans, Marshall and Wake seamount groups (western Pacific Ocean) that originated in this South Pacific Isotopic and Thermal Anomaly (SOPITA). The range and values of isotope ratios of the Cretaceous seamount data are similar to those of the island chains of Samoa, Tahiti, Marquesas and Cook/Austral in the SOPITA. These define two major mantle components suggesting that isotopically extreme lavas have been produced at SOPITA for at least 120 Ma. Shallow bathymetry, and weakened lithosphere beneath some of the seamounts studied suggests that at least some of the thermal effects prevailed during the Cretaceous as well. These data, in the context of published data, suggest: 1. (1)|SOPITA is a long-lived feature, and enhanced heat transfer into the lithosphere and isotopically anomalous mantle appear to be an intrinsic characteristic of the anomaly. 2. (2)|The less pronounced depth anomaly during northwesterly plate motion suggests that some of the expressions of SOPITA may be controlled by the direction of plate motion. Motion parallel to the alignment of SOPITA hot spots focusses the heat (and chemical input into the lithosphere) on a smaller cross section than oblique motion. 3. (3)|The lithosphere in the eastern and central SOPITA appears to have lost its original depleted mantle characteristics, probably due to enhanced plume/lithosphere interaction, and it is dominated by isotopic compositions derived from plume materials. 4. (4)|We speculate (following D.L. Anderson) that the origin of the SOPITA, and possibly the DUPAL anomaly is largely due to focussed subduction through long periods of the geological history of the earth, creating a heterogeneous distribution of recycled components in the lower mantle

  16. A spectacular nitrogen isotope anomaly in Bencubbin

    NASA Technical Reports Server (NTRS)

    Prombo, C. A.; Clayton, R. N.

    1985-01-01

    Results of isotopic measurements on an unusual stony-iron meteorite named Bencubbin, which was found in Western Australia in 1930, are reported. Nitrogen from both the metallic and stony parts of the Bencubbin meteorite was analyzed, and in both materials large excesses of (15)N were found, resulting in values of the (14)N/(15)N abundance ratios as low as 137. That is, (15)N is enriched in Bencubbin by about a factor of two relative to terrestrial nitrogen. This is the largest (15)N enrichment of any known natural material. The effect is so large that chemical processes are probably inadequate to account for it. Nuclear processes which may be responsible for the anomalous isotope abundance are discussed.

  17. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1978-01-01

    The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

  18. Palladium Isotopic Evidence for Nucleosynthetic and Cosmogenic Isotope Anomalies in IVB Iron Meteorites

    NASA Astrophysics Data System (ADS)

    Mayer, Bernhard; Wittig, Nadine; Humayun, Munir; Leya, Ingo

    2015-08-01

    The origin of ubiquitous nucleosynthetic isotope anomalies in meteorites may represent spatial and/or temporal heterogeneity in the sources that supplied material to the nascent solar nebula, or enhancement by chemical processing. For elements beyond the Fe peak, deficits in s-process isotopes have been reported in some (e.g., Mo, Ru, W) but not all refractory elements studied (e.g., Os) that, among the iron meteorites, are most pronounced in IVB iron meteorites. Palladium is a non-refractory element in the same mass region as Mo and Ru. In this study, we report the first precise Pd isotopic abundances from IVB irons to test the mechanisms proposed for the origin of isotope anomalies. First, this study determined the existence of a cosmogenic neutron dosimeter from the reaction 103Rh(n, β-)104Pd in the form of excess 104Pd, correlated with excess 192Pt, in IVB irons. Second, all IVB irons show a deficit of the s-process only isotope 104Pd (\\varepsilon 104Pd = -0.48 ± 0.24), an excess of the r-only isotope 110Pd (\\varepsilon 110Pd = +0.46 ± 0.12), and no resolvable anomaly in the p-process 102Pd (\\varepsilon 102Pd = +1 ± 1). The magnitude of the Pd isotope anomaly is about half that predicted from a uniform depletion of the s-process yields from the correlated isotope anomalies of refractory Mo and Ru. The discrepancy is best understood as the result of nebular processing of the less refractory Pd, implying that all the observed nucleosynthetic anomalies in meteorites are likely to be isotopic relicts. The Mo-Ru-Pd isotope systematics do not support enhanced rates of the 22Ne(α,n)25Mg neutron source for the solar system s-process.

  19. Iron isotope anomalies. [in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Voelkening, J.; Papanastassiou, D. A.

    1989-01-01

    Precise determinations of the Fe isotope abundances yield identical results for a terrestrial standard and for samples of carbonaceous meteorites. Fe-54/Fe-56 = 0.062669; Fe-57/Fe-56 = 0.023261 + or - 0.000002; and Fe-58/Fe-56 = 0.0031132 + or - 0.0000011 are found. Refractory element-rich inclusions from the Allende carbonaceous meteorite yield hints of deficits in Fe-57/Fe-56 of up to -3.9 + or - 2.6 parts in 10,000 and a hint of excess in Fe-58/Fe-56 of up to 27 + or - 11 parts in 10,000. One special (FUN) inclusion shows a large excess of 2.9 percent, uniquely attributable to Fe-58. This excess correlates with large excesses in the same inclusion in the neutron-rich isotopes Ca-48, Ti-50 and Cr-54. These results strengthen the evidence for an exotic nucleosynthetic component produced by neutron-rich, statistical equilibrium burning, and injected into the interstellar medium.

  20. Advanced Mass Spectrometers for Hydrogen Isotope Analyses

    SciTech Connect

    Chastagner, P.

    2001-08-01

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

  1. NEUTRON-RICH CHROMIUM ISOTOPE ANOMALIES IN SUPERNOVA NANOPARTICLES

    SciTech Connect

    Dauphas, N.; Remusat, L.; Papanastassiou, D. A.; Guan, Y.; Ma, C.; Eiler, J. M.; Chen, J. H.; Roskosz, M.; Stodolna, J.

    2010-09-10

    Neutron-rich isotopes with masses near that of iron are produced in Type Ia and II supernovae (SNeIa and SNeII). Traces of such nucleosynthesis are found in primitive meteorites in the form of variations in the isotopic abundance of {sup 54}Cr, the most neutron-rich stable isotope of chromium. The hosts of these isotopic anomalies must be presolar grains that condensed in the outflows of SNe, offering the opportunity to study the nucleosynthesis of iron-peak nuclei in ways that complement spectroscopic observations and can inform models of stellar evolution. However, despite almost two decades of extensive search, the carrier of {sup 54}Cr anomalies is still unknown, presumably because it is fine grained and is chemically labile. Here, we identify in the primitive meteorite Orgueil the carrier of {sup 54}Cr anomalies as nanoparticles (<100 nm), most likely spinels that show large enrichments in {sup 54}Cr relative to solar composition ({sup 54}Cr/{sup 52}Cr ratio >3.6 x solar). Such large enrichments in {sup 54}Cr can only be produced in SNe. The mineralogy of the grains supports condensation in the O/Ne-O/C zones of an SNII, although a Type Ia origin cannot be excluded. We suggest that planetary materials incorporated different amounts of these nanoparticles, possibly due to late injection by a nearby SN that also delivered {sup 26}Al and {sup 60}Fe to the solar system. This idea explains why the relative abundance of {sup 54}Cr and other neutron-rich isotopes vary between planets and meteorites. We anticipate that future isotopic studies of the grains identified here will shed new light on the birth of the solar system and the conditions in SNe.

  2. More on Ru Endemic Isotope Anomalies in Meteorites

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.; Chen, J. H.; Wasserburg, G. J.

    2004-01-01

    We reported last year on endemic isotope anomalies for Ru in iron meteorites, pallasites, ordinary chondrites, and on a whole-rock sample of Allende. We have extended the Ru measurements to more meteorites, to refractory Ca-Al-rich inclusions (CAI) from Allende, and to a whole rock sample of Murchison (CM2). In a companion abstract we report on new measurements for the Mo isotopes, in some of the same samples. There has been a renewed interest in searching for isotope anomalies in this nuclide region, as Ru and Mo include many isotopes from r-, s-, and p-process nucleosynhesis. Furthermore, the Ru and Mo p-process isotopes show atypically high abundances, which have been hard to explain through the standard nucleosynthetic processes. Effects are possible in Ru-98 and Ru-99 from Tc-98 (with a poorly known t(sub 1/2)=4.2 to 10Ma) and from Tc-99 (t(sub 1/2)=0.21Ma). Natural Tc is now extinct on Earth due to the short half-lives, but may have been present in the early solar system. Both radiogenic and general isotope anomalies are important in understanding the processes for the formation of the early solar system. The current emphasis on Ru and Mo is also the result of the development of Negative-ion Thermal Ionization Mass Spectrometry and of Multiple-Collector, Inductively-Coupled-Mass-Spectrometry. We have also developed specific chemical siparation techniques for Ru, which eliminated mass interference effects.

  3. Neutron-poor Nickel Isotope Anomalies in Meteorites

    NASA Astrophysics Data System (ADS)

    Steele, Robert C. J.; Coath, Christopher D.; Regelous, Marcel; Russell, Sara; Elliott, Tim

    2012-10-01

    We present new, mass-independent, Ni isotope data for a range of bulk chondritic meteorites. The data are reported as ɛ60Ni58/61, ɛ62Ni58/61, and ɛ64Ni58/61, or the parts per ten thousand deviations from a terrestrial reference, the NIST SRM 986 standard, of the 58Ni/61Ni internally normalized 60Ni/61Ni, 62Ni/61Ni, and 64Ni/61Ni ratios. The chondrites show a range of 0.15, 0.29, and 0.84 in ɛ60Ni58/61, ɛ62Ni58/61, and ɛ64Ni58/61 relative to a typical sample precision of 0.03, 0.05, and 0.08 (2 s.e.), respectively. The carbonaceous chondrites show the largest positive anomalies, enstatite chondrites have approximately terrestrial ratios, though only EH match Earth's composition within uncertainty, and ordinary chondrites show negative anomalies. The meteorite data show a strong positive correlation between ɛ62Ni58/61 and ɛ64Ni58/61, an extrapolation of which is within the error of the average of previous measurements of calcium-, aluminium-rich inclusions. Moreover, the slope of this bulk meteorite array is 3.003 ± 0.166 which is within the error of that expected for an anomaly solely on 58Ni. We also determined to high precision (~10 ppm per AMU) the mass-dependent fractionation of two meteorite samples which span the range of ɛ62Ni58/61 and ɛ64Ni58/61. These analyses show that "absolute" ratios of 58Ni/61Ni vary between these two samples whereas those of 62Ni/61Ni and 64Ni/61Ni do not. Thus, Ni isotopic differences seem most likely explained by variability in the neutron-poor 58Ni, and not correlated anomalies in the neutron-rich isotopes, 62Ni and 64Ni. This contrasts with previous inferences from mass-independent measurements of Ni and other transition elements which invoked variable contributions of a neutron-rich component. We have examined different nucleosynthetic environments to determine the possible source of the anomalous material responsible for the isotopic variations observed in Ni and other transition elements within bulk samples. We find

  4. NEUTRON-POOR NICKEL ISOTOPE ANOMALIES IN METEORITES

    SciTech Connect

    Steele, Robert C. J.; Coath, Christopher D.; Regelous, Marcel; Elliott, Tim; Russell, Sara

    2012-10-10

    We present new, mass-independent, Ni isotope data for a range of bulk chondritic meteorites. The data are reported as {epsilon}{sup 60}Ni{sub 58/61}, {epsilon}{sup 62}Ni{sub 58/61}, and {epsilon}{sup 64}Ni{sub 58/61}, or the parts per ten thousand deviations from a terrestrial reference, the NIST SRM 986 standard, of the {sup 58}Ni/{sup 61}Ni internally normalized {sup 60}Ni/{sup 61}Ni, {sup 62}Ni/{sup 61}Ni, and {sup 64}Ni/{sup 61}Ni ratios. The chondrites show a range of 0.15, 0.29, and 0.84 in {epsilon}{sup 60}Ni{sub 58/61}, {epsilon}{sup 62}Ni{sub 58/61}, and {epsilon}{sup 64}Ni{sub 58/61} relative to a typical sample precision of 0.03, 0.05, and 0.08 (2 s.e.), respectively. The carbonaceous chondrites show the largest positive anomalies, enstatite chondrites have approximately terrestrial ratios, though only EH match Earth's composition within uncertainty, and ordinary chondrites show negative anomalies. The meteorite data show a strong positive correlation between {epsilon}{sup 62}Ni{sub 58/61} and {epsilon}{sup 64}Ni{sub 58/61}, an extrapolation of which is within the error of the average of previous measurements of calcium-, aluminium-rich inclusions. Moreover, the slope of this bulk meteorite array is 3.003 {+-} 0.166 which is within the error of that expected for an anomaly solely on {sup 58}Ni. We also determined to high precision ({approx}10 ppm per AMU) the mass-dependent fractionation of two meteorite samples which span the range of {epsilon}{sup 62}Ni{sub 58/61} and {epsilon}{sup 64}Ni{sub 58/61}. These analyses show that 'absolute' ratios of {sup 58}Ni/{sup 61}Ni vary between these two samples whereas those of {sup 62}Ni/{sup 61}Ni and {sup 64}Ni/{sup 61}Ni do not. Thus, Ni isotopic differences seem most likely explained by variability in the neutron-poor {sup 58}Ni, and not correlated anomalies in the neutron-rich isotopes, {sup 62}Ni and {sup 64}Ni. This contrasts with previous inferences from mass-independent measurements of Ni and other

  5. On isotopic anomalies in samarium. [in Allende meteorite

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1979-01-01

    The solar isotopic composition of Sm is decomposed into s, r, and p components. The anomaly pattern discovered by Lugmair et al. (1978) in EK1-04 Allende inclusion can be presented as a fractionation of the average s-pattern from the average r-pattern. This representation requires a fractionation of 0.029%/(amu) and either (1) a 0.42% deficiency of s relative to r and a 0.15% deficiency of p relative to r, or (2) a 0.42% excess of r relative to s and a 0.27% excess of p relative to s. The nature of this anomaly suggest a systematic physical fractionation of r, s, and p nuclei from each other in the initial condition leading to EK1-04. A neighboring supernova injection would not be expected to produce this anomaly.

  6. Mass Fractionation Laws, Mass-Independent Effects, and Isotopic Anomalies

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Schauble, Edwin A.

    2016-06-01

    Isotopic variations usually follow mass-dependent fractionation, meaning that the relative variations in isotopic ratios scale with the difference in mass of the isotopes involved (e.g., δ17O ≈ 0.5×δ18O). In detail, however, the mass dependence of isotopic variations is not always the same, and different natural processes can define distinct slopes in three-isotope diagrams. These variations are subtle, but improvements in analytical capabilities now allow precise measurement of these effects and make it possible to draw inferences about the natural processes that caused them (e.g., reaction kinetics versus equilibrium isotope exchange). Some elements, in some sample types, do not conform to the regularities of mass-dependent fractionation. Oxygen and sulfur display a rich phenomenology of mass-independent fractionation, documented in the laboratory, in the rock record, and in the modern atmosphere. Oxygen in meteorites shows isotopic variations that follow a slope-one line (δ17O ≈ δ18O) whose origin may be associated with CO photodissociation. Sulfur mass-independent fractionation in ancient sediments provides the tightest constraint on the oxygen partial pressure in the Archean and the timing of Earth's surface oxygenation. Heavier elements also show departures from mass fractionation that can be ascribed to exotic effects associated with chemical reactions such as magnetic effects (e.g., Hg) or the nuclear field shift effect (e.g., U or Tl). Some isotopic variations in meteorites and their constituents cannot be related to the terrestrial composition by any known process, including radiogenic, nucleogenic, and cosmogenic effects. Those variations have a nucleosynthetic origin, reflecting the fact that the products of stellar nucleosynthesis were not fully homogenized when the Solar System formed. Those anomalies are found at all scales, from nanometer-sized presolar grains to bulk terrestrial planets. They can be used to learn about stellar

  7. 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.

  8. Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

    NASA Technical Reports Server (NTRS)

    Loss, R. D.; Lugmair, G. W.; Davis, A. M.; Macpherson, G. J.

    1994-01-01

    The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

  9. Titanium isotopic anomalies in hibonites from the Murchison carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Ireland, T. R.; Compston, W.; Heydegger, H. R.

    1985-09-01

    The isotopic compositions of titanium in eight grains of hibonite (CaAl12O19) from the carbonaceous chondrite Murchison have been determined by high precision secondary ion mass spectrometry using an ion microprobe. The titanium in the hibonites varies greatly in Ti-50 from about -42 to +8 permil (relative to terrestrial) with smaller (up to 4 permil), but clearly resolvable, effects in Ti-46 and Ti-48. These results confirm the presence of widespread negative anomalies suggested by the results of Hutcheon et al. (1983) on hibonites from Murchison. The magnitude of these variations seems explicable only in terms of nucleogenic processes which produced extremely variable titanium isotopic abundances in the hibonite source materials. The hibonites evidently did not participate to the same extent as most material in the mixing and homogenisation processes that accompanied the formation and later evolution of the solar system.

  10. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1991-05-08

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

  11. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1993-03-30

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

  12. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, James W.

    1993-01-01

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

  13. Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

    PubMed

    Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H

    2010-11-23

    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

  14. Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

    PubMed Central

    Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R.; Thiemens, Mark H.

    2010-01-01

    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

  15. Apparatus for separating and recovering hydrogen isotopes

    DOEpatents

    Heung, Leung K.

    1994-01-01

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

  16. Oxidation of hydrogen isotopes over honeycomb catalysts

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  17. Toward magnetic trapping of isotopes of hydrogen

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  18. Review of hydrogen isotope permeability through materials

    SciTech Connect

    Steward, S.A.

    1983-08-15

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

  19. Progress towards trapping of atomic hydrogen isotopes

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  20. METHOD OF SEPARATING HYDROGEN ISOTOPES

    DOEpatents

    Salmon, O.N.

    1958-12-01

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

  1. Isotope effects of hydrogen and atom tunnelling

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  2. The isotopic homogeneity in the early solar system: Revisiting the CAI oxygen isotopic anomaly

    NASA Astrophysics Data System (ADS)

    Ozima, M.; Yamada, A.

    2009-12-01

    Since the first discovery of the mass-independently fractionated oxygen isotopes in anhydrous, high temperature Ca-Al rich inclusion minerals in carbonaceous meteorites (CAIs) by Clayton et al. (1), their common occurrence in primitive meteorites has generally been regarded to reflect some fundamental process prevalent in the early solar nebula. The CAI oxygen isotopic composition is uniquely characterized by (i) large mass independent isotopic fractionation and (ii) their isotopic data in an oxygen three isotope plot (δ17O - δ18O (δ17O ≡ {(17O/16O)/(17O/16O)SMOW - 1} × 1000) yield nearly a straight line with a slope 1.0. In establishing these characteristics, ion microprobe analyses has played a central role, especially an isotopic mapping technique (isotopography) was crucial (e.g., 2). The extraordinary oxygen isotopic ratio in CAIs is widely attributed to the self-shielding absorption of UV radiation in CO, one of the dominant chemical compounds in the early solar nebula (3). However, the self-shielding scenario necessarily leads to the unusual prediction that a mean solar oxygen isotopic composition differs from most of planetary bodies including Earth, Moon, and Mars. If the self-shielding process were indeed responsible to the CAI oxygen isotopic anomaly, this would require a fundamental revision of the current theory of the origin of the solar system, which generally assumes the initial total vaporization of nebula material to give rise to isotopic homogenization. The GENESIS mission launched in 2001(4), which collected oxygen in the solar wind was hoped to resolve the isotopic composition of the Sun. However, because of difficulties in correcting for instrumental and more importantly for intrinsic isotopic fractionation between the SW and the Sun, a final answer is yet to be seen (5). Here, we show on the basis of the oxygen isotopic fractionation systematics that the self shielding hypothesis cannot explain the key characteristics of the CAI oxygen

  3. Toward magnetic trapping of isotopes of hydrogen

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  4. Strong water isotopic anomalies in the martian atmosphere: probing current and ancient reservoirs.

    PubMed

    Villanueva, G L; Mumma, M J; Novak, R E; Käufl, H U; Hartogh, P; Encrenaz, T; Tokunaga, A; Khayat, A; Smith, M D

    2015-04-10

    We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep. PMID:25745065

  5. Strong water isotopic anomalies in the martian atmosphere: Probing current and ancient reservoirs

    NASA Astrophysics Data System (ADS)

    Villanueva, G. L.; Mumma, M. J.; Novak, R. E.; Käufl, H. U.; Hartogh, P.; Encrenaz, T.; Tokunaga, A.; Khayat, A.; Smith, M. D.

    2015-04-01

    We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth’s ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep.

  6. Strong Water Isotopic Anomalies in the Martian Atmosphere: Probing Current and Ancient Reservoirs

    NASA Technical Reports Server (NTRS)

    Villanueva, G. L.; Mumma, M. J.; Novak, R. E.; Käufl, H. U.; Hartogh, P.; Encrenaz, T.; Tokunaga, A.; Khayat, A.; Smith, M. D.

    2015-01-01

    We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep.

  7. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

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

  8. Collision integrals for isotopic hydrogen molecules.

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  9. Hydrogen isotope composition of magmatic water

    SciTech Connect

    Taylor, B.E. )

    1992-01-01

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

  10. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

    PubMed

    Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

    2014-08-19

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere. PMID:25092338

  11. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere

    PubMed Central

    Shaheen, Robina; Abaunza, Mariana M.; Jackson, Teresa L.; McCabe, Justin; Savarino, Joël; Thiemens, Mark H.

    2014-01-01

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984–2001) showed the highest S-isotopic anomalies (Δ33S = +1.66‰ and Δ36S = +2‰) in a nonvolcanic (1998–1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997–1998)-induced changes in troposphere–stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ36S = −0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere. PMID:25092338

  12. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    1990-01-01

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

  13. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    1991-01-01

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

  14. Hydrogen isotope separation utilizing bulk getters

    DOEpatents

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

    1991-08-20

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

  15. Water-hydrogen isotope exchange process analysis

    SciTech Connect

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

    2008-07-15

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

  16. 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).

  17. On strontium isotopic anomalies and odd-A p-process abundances. [in solar system

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1978-01-01

    Several aspects of the nucleosynthesis of Sr isotopes are considered in an attempt to shed light on the problem of the Sr isotopic anomalies discovered in an inclusion of the Allende meteorite. Decomposition of the Sr isotopes into average r-, s-, and p-process nucleosynthetic classes is performed. It is suggested that the Allende inclusion most likely has an excess of s-process Sr and that the initial Sr-87/Sr-86 isotopic ratio is probably slightly more primitive than basaltic achondrites. The results also show that Sn-115 is mostly due to the r-process and that odd-A yields are very small. It is concluded that if the Sr anomaly in the inclusion is an average s enhancement, it argues somewhat in favor of a model of gas/dust fractionation of s and r isotopes during accumulation of the inclusion parent in the protosolar cloud.

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

    SciTech Connect

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

    2015-03-15

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

  19. Hydrogen in vanadium: Site occupancy and isotope effects

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    SciTech Connect

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

    1995-05-01

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

  1. Endemic Ru Isotopic Anomalies in Iron Meteorites and in Allende

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.

    2003-01-01

    Small variations for Mo isotopes have been observed recently in the Allende meteorite and in iron meteorites, mesosiderites, and pallasites, using ICPMS. Large effects for Mo have been reported for leaches of Orgueil and in SiC and graphite from Murchison. Variations for Mo in bulk Allende and in Murchison have also been presented by NTIMS. Effects in Ru isotopes can define further the preserved exotic r, s, and p contributions in this mass region, and possible effects in Ru-98 and Ru-99 from Tc-98 (4.2 Ma half-life) and Tc-99 (0.21 Ma half-life). Previous attempts at determination of Ru isotopes yielded no resolved effects. The present work represents a substantial improvement in precision over the earlier work. Chemical and mass spectrometric analytical techniques are presented to determine the Ru isotope compositions in terrestrial standards and in meteorites.

  2. Carbon Isotopic tests on the Origins of the Shuram Anomaly from the San Juan Fm., Peru

    NASA Astrophysics Data System (ADS)

    Hodgin, E. B.

    2015-12-01

    Carbon isotope anomalies are associated with perturbations to the carbon cycle that offer insight into the geochemical evolution of the Earth. The largest Carbon isotope anomaly in earth history is the Shuram, which remains poorly understood in spite of being linked to the oxygenation of earth, the rise of metazoans, and a complete reorganization of the carbon cycle. From a basin transect of the carbonate-dominated San Juan Formation in southern Peru, we present evidence for the first clear example of the Shuram isotope anomaly in South America. Unique to this succession are ~140 meters of organic-rich black shale within the anomaly, containing as much as 4% TOC. Preliminary data from the organic-rich black shales of the San Juan Fm. confirm that δ13Corg is relatively invariant and does not covary with δ13Ccarb. These observations are consistent with other Shuram sections and support various models: an exogenous carbon source, an enlarged dissolved organic carbon pool, as well as authigenic carbonate production in organic-rich anoxic sediments. Critical tests of these models have been complicated by a paucity of organics in Shuram facies worldwide. Further analyses of the robust organics from the Shuram facies of the San Juan Fm. therefore hold promise in shedding light on the origin of the Shuram isotope anomaly and critical earth history events to which it has been linked.

  3. Equations of state and phase diagrams of hydrogen isotopes

    SciTech Connect

    Urlin, V. D.

    2013-11-15

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

  4. Anomalies.

    ERIC Educational Resources Information Center

    Online-Offline, 1999

    1999-01-01

    This theme issue on anomalies includes Web sites, CD-ROMs and software, videos, books, and additional resources for elementary and junior high school students. Pertinent activities are suggested, and sidebars discuss UFOs, animal anomalies, and anomalies from nature; and resources covering unexplained phenonmenas like crop circles, Easter Island,…

  5. Hydrogen isotope systematics of submarine basalts

    USGS Publications Warehouse

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

    1984-01-01

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

  6. 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.

  7. Negligible Isotopic Effect on Dissociation of Hydrogen Bonds.

    PubMed

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

    2016-03-31

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

  8. Isotopic Anomalies in Organic Nanoglobules from Comet 81P/Wild 2: Comparison to Murchison Nanoglobules and Isotopic Anomalies Induced in Terrestrial Organics by Electron Irradiation

    SciTech Connect

    De Gregorio, B.; Stroud, R; Nittler, L; Alexander, C; Kilcoyne, A; Zega, T

    2010-01-01

    Nanoglobules are a form of organic matter found in interplanetary dust particles and primitive meteorites and are commonly associated with {sup 15}N and D isotopic anomalies that are suggestive of interstellar processes. We report the discovery of two isotopically-anomalous organic globules from the Stardust collection of particles from Comet 81P/Wild 2 and compare them with nanoglobules from the Murchison CM2 meteorite. One globule from Stardust Cometary Track 80 contains highly aromatic organic matter and a large {sup 15}N anomaly ({delta}{sup 15}N = 1120{per_thousand}). Associated, non-globular, organic matter from this track is less enriched in {sup 15}N and contains a mixture of aromatic and oxidized carbon similar to bulk insoluble organic material (IOM) from primitive meteorites. The second globule, from Cometary Track 2, contains non-aromatic organic matter with abundant nitrile ({single_bond}C{triple_bond}N) and carboxyl ({single_bond}COOH) functional groups. It is significantly enriched in D ({delta}D = 1000{per_thousand}) but has a terrestrial {sup 15}N/{sup 14}N ratio. Experiments indicate that similar D enrichments, unaccompanied by {sup 15}N fractionation, can be reproduced in the laboratory by electron irradiation of epoxy or cyanoacrylate. Thus, a terrestrial origin for this globule cannot be ruled out, and, conversely, exposure to high-energy electron irradiation in space may be an important factor in producing D anomalies in organic materials. For comparison, we report two Murchison globules: one with a large {sup 15}N enrichment and highly aromatic chemistry analogous to the Track 80 globule and the other only moderately enriched in {sup 15}N with IOM-like chemistry. The observation of organic globules in Comet 81P/Wild 2 indicates that comets likely sampled the same reservoirs of organic matter as did the chondrite parent bodies. The observed isotopic anomalies in the globules are most likely preserved signatures of low temperature (<10 K

  9. Isotopic anomalies in organic nanoglobules from Comet 81P/Wild 2: Comparison to Murchison nanoglobules and isotopic anomalies induced in terrestrial organics by electron irradiation

    NASA Astrophysics Data System (ADS)

    De Gregorio, Bradley T.; Stroud, Rhonda M.; Nittler, Larry R.; Alexander, Conel M. O.'D.; Kilcoyne, A. L. David; Zega, Thomas J.

    2010-08-01

    Nanoglobules are a form of organic matter found in interplanetary dust particles and primitive meteorites and are commonly associated with 15N and D isotopic anomalies that are suggestive of interstellar processes. We report the discovery of two isotopically-anomalous organic globules from the Stardust collection of particles from Comet 81P/Wild 2 and compare them with nanoglobules from the Murchison CM2 meteorite. One globule from Stardust Cometary Track 80 contains highly aromatic organic matter and a large 15N anomaly (δ 15N = 1120‰). Associated, non-globular, organic matter from this track is less enriched in 15N and contains a mixture of aromatic and oxidized carbon similar to bulk insoluble organic material (IOM) from primitive meteorites. The second globule, from Cometary Track 2, contains non-aromatic organic matter with abundant nitrile ( sbnd C tbnd N) and carboxyl ( sbnd COOH) functional groups. It is significantly enriched in D (δD = 1000‰) but has a terrestrial 15N/ 14N ratio. Experiments indicate that similar D enrichments, unaccompanied by 15N fractionation, can be reproduced in the laboratory by electron irradiation of epoxy or cyanoacrylate. Thus, a terrestrial origin for this globule cannot be ruled out, and, conversely, exposure to high-energy electron irradiation in space may be an important factor in producing D anomalies in organic materials. For comparison, we report two Murchison globules: one with a large 15N enrichment and highly aromatic chemistry analogous to the Track 80 globule and the other only moderately enriched in 15N with IOM-like chemistry. The observation of organic globules in Comet 81P/Wild 2 indicates that comets likely sampled the same reservoirs of organic matter as did the chondrite parent bodies. The observed isotopic anomalies in the globules are most likely preserved signatures of low temperature (<10 K) chemistry in the interstellar medium or perhaps the outer regions of the solar nebula. In other

  10. 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.

  11. A superior process for forming titanium hydrogen isotopic films

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

  12. Carbon dioxide and oxygen isotope anomalies in the mesosphere and stratosphere

    SciTech Connect

    Thiemens, M.H.; Jackson, T.; Zipf, E.C.

    1995-11-10

    Isotopic ({delta}{sup 17}O and {delta}{sup 18}O) measurements of stratospheric and mesospheric carbon dioxide (CO{sub 2}) and oxygen (O{sub 2}), along with trace species concentrations (N{sub 2}O, CO, and CO{sub 2}), were made in samples collected from a rocket-borne cryogenic whole air sampler. A large mass-independent isotopic anomaly was observed in CO{sub 2}, which may in part derive from photochemical coupling to ozone (O{sub 3}). The data also require an additional isotopic fractionation process, which is presently unidentified. Mesospheric O{sub 2} isotope ratios differed from those in the troposphere and stratosphere. The cause of this isotopic variation in O{sub 2} is presently unknown. The inability to account for these observations represents a fundamental gap in the understanding of the O{sub 2} chemistry in the stratosphere and mesosphere. 28 refs., 2 figs., 1 tab.

  13. Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization.

    PubMed

    Salim, Michael A; Willow, Soohaeng Yoo; Hirata, So

    2016-05-28

    Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D2O ice greater than that of H2O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born-Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of

  14. Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization

    NASA Astrophysics Data System (ADS)

    Salim, Michael A.; Willow, Soohaeng Yoo; Hirata, So

    2016-05-01

    Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D2O ice greater than that of H2O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born-Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of

  15. Isotopic Anomalies in a Uranium Cluster Formed by Lais

    NASA Astrophysics Data System (ADS)

    van de Walle, J.; Tarento, R. J.; Joyes, P.

    A study of a Au-U liquid alloy ion source (LAIS) where uranium is enriched in its lighter element (20% 235U, 80% 238U) has been performed by high resolution mass spectrometry. Monoatomic species Au+, Au2+, U2+, U3+ and polyatomic species Au+n, Up+n, AunU+ are observed. The monoatomic results are well explained by the Kingham postionization process. Au+n and AunU+ species present an interesting odd-even effect characteristic of monovalent elements. The main result of this preliminary letter is a heteroisotope anomaly which appears in U+2, U+3 and U4+3 emission where only homoisotopes are detected. A similar phenomenon was reported for Cu+2 and Ge+2 in a previous work and was attributed to a higher state of excitation of emitted heteroisotope aggregates which explode as they fly to the collector.1,2

  16. Oxygen Isotope Anomalies in Orgueil Corundum: Confirmation of Presolar Origin

    NASA Astrophysics Data System (ADS)

    Huss, G. R.; Hutcheon, I. D.; Fahey, A. J.; Wasserburg, G. J.

    1993-07-01

    In a study of Mg isotopes in oxide grains from an Orgueil SiC-spinel-rich residue, [1] reported a corundum grain with ^26Mg*/^27Al = 8.9 x 10^-4, a value ~18 times greater than the canonical 5 x 10^-5 value characteristic of refractory phases formed in the solar nebula. Comparable ratios had previously been found only in carbon-rich interstellar materials, SiC and graphite, [2] leading [1] to suggest that Orgueil corundum B is a pre-solar oxide grain. Subsequently, [3] discovered Murchison corundum 83-5 with a sirnilar ^26Mg*/^27Al of 8.7 x 10^-4; the very unusual oxygen isotope composition (delta^17O = 1072 +- 59 per mil, delta^18O = -244 per mil) led [3] to conclude 83-5 is an interstellar oxide grain. The Panurge ion probe was used to determine ^170/^160 and ^180/^160 ratios in 27 Orgueil oxide grains--16 corundum, 2 hibonite, and 9 spinel--and in 6 Allende spinels. Orgueil corundum B has an extreme ^17O excess (delta^17O = 1394 +- 178 per mil (2sigma(mean)) and a hint of an ^18O depletion (delta^18O = -65 +- 64 per mil) (Fig. 1). The extraordinary enrichments in ^26Mg* and ^17O identify Orgueil B as an interstellar oxide grain. Orgueil B and Murchison 83-5 have remarkably similar O- and Mg-isotope compositions. Red giant stars are enriched in ^17O with ^17O/^18O >~ 1 [4], suggesting these stars are a likely source of the interstellar corundum. Production of ^26Al during H-burning in AGB stars also appears to account for the ^26Mg* excess [5,6]. Condensation of corundum in the circumstellar envelope must occur before dredge up of processed material from the stellar interior decreases ^17O/^16O and creates a C-rich atmosphere. The oxygen isotope compositions of the remaining oxide grains fall into three groups (Fig. 1). All but six corundums and one Orgueil spinel exhibit ^16O excesses and lie along the ^16O-mixing line with compositions similar to those of corundum and spinel from Murchison LS, LU, and CFO(sub)c [7]. Data from Allende spinels cluster about a

  17. Calcium-48 isotopic anomalies in bulk chondrites and achondrites: Evidence for a uniform isotopic reservoir in the inner protoplanetary disk

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Chen, James H.; Zhang, Junjun; Papanastassiou, Dimitri A.; Davis, Andrew M.; Travaglio, Claudia

    2014-12-01

    Thermal ionization mass spectrometry (TIMS) was used to measure the calcium isotopic compositions of carbonaceous, ordinary, enstatite chondrites as well as eucrites and aubrites. We find that after correction for mass-fractionation by internal normalization to a fixed 42Ca/44Ca ratio, the 43Ca/44Ca and 46Ca/44Ca ratios are indistinguishable from terrestrial ratios. In contrast, the 48Ca/44Ca ratios show significant departure from the terrestrial composition (from -2 ε in eucrites to +4 ε in CO and CV chondrites). Isotopic anomalies in ε48Ca correlate with ε50Ti: ε 48Ca=(1.09±0.11)×ε 50Ti+(0.03±0.14). Further work is needed to identify the carrier phase of 48Ca-50Ti anomalies but we suggest that it could be perovskite and that the stellar site where these anomalies were created was also responsible for the nucleosynthesis of the bulk of the solar system inventory of these nuclides. The Earth has identical 48Ca isotopic composition to enstatite chondrites (EH and EL) and aubrites. This adds to a long list of elements that display nucleosynthetic anomalies at a bulk planetary scale but show identical or very similar isotopic compositions between enstatite chondrites, aubrites, and Earth. This suggests that the inner protoplanetary disk was characterized by a uniform isotopic composition (IDUR for Inner Disk Uniform Reservoir), sampled by enstatite chondrites and aubrites, from which the Earth drew most of its constituents. The terrestrial isotopic composition for 17O, 48Ca, 50Ti, 62Ni, and 92Mo is well reproduced by a mixture of 91% enstatite, 7% ordinary, and 2% carbonaceous chondrites. The Earth was not simply made of enstatite chondrites but it formed from the same original material that was later modified by nebular and disk processes. The Moon-forming impactor probably came from the same region as the other embryos that made the Earth, explaining the strong isotopic similarity between lunar and terrestrial rocks.

  18. On Hydrogen and Helium embrittlement in Isotopic tailoring Experiments

    SciTech Connect

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

    2000-09-01

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

  19. Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere

    PubMed Central

    Lin, Ying; Clayton, Robert N.; Huang, Lin; Nakamura, Noboru; Lyons, James R.

    2013-01-01

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ17O and δ18O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ17O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ17O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ17O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had 17Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

  20. Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere.

    PubMed

    Lin, Ying; Clayton, Robert N; Huang, Lin; Nakamura, Noboru; Lyons, James R

    2013-09-24

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003-2005 at Alert station, Canada (82°30'N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ(17)O and δ(18)O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003-2005. An oxygen isotopic anomaly of Δ(17)O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ(17)O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930-1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ(17)O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had (17)Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

  1. Interactions of Hydrogen Isotopes and Oxides with Metal Tubes

    SciTech Connect

    Glen R. Longhurst

    2008-08-01

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

  2. Interactions of hydrogen isotopes and oxides with metal tubes

    SciTech Connect

    Longhurst, G. R.; Cleaver, J.

    2008-07-15

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

  3. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    SciTech Connect

    Aldridge, F.T.

    1984-05-09

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

  4. Experimental stand for studies of hydrogen isotopes permeation

    SciTech Connect

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

    2008-07-15

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

  5. 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.

  6. Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species

    NASA Astrophysics Data System (ADS)

    Morin, S.; Sander, R.; Savarino, J.

    2010-12-01

    The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3-) or hydrogen peroxyde (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. We present results from numerical simulations carried out using the atmospheric chemistry box model (CAABA/MECCA) to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model confirms that diurnal variations in Δ17O of NOx are well predicted by the photochemical steady-state relationship during the day, but that at night a different approach must be employed (i.e. "fossilization" of the Δ17O of NOx as soon as the photolytical lifetime of NOx drops below ca. 5 min). We quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2 under the various environmental conditions analyzed, which is of particular relevance to larger-scale implementations of Δ17O where high computational costs cannot be afforded.

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

    PubMed Central

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

    2003-01-01

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

  8. The sp-process and Allende isotope anomalies in calcium and titanium

    NASA Astrophysics Data System (ADS)

    Harris, M. J.

    1983-01-01

    The goal of the study described here is to show that partial nuclear destruction of the Ca isotopes can reproduce the EK-1-4-1 pattern and can simultaneously produce the Ti anomaly observed in that inclusion. The parameterized approach adopted here yields little information about a likely stellar site. Considerations of time scale and proton density, however, both point to a hydrostatic O burning zone, with which the required s-process-like initial composition is compatible. The temperatures involved, however, are considerably lower than those estimated by Arnett (1977) and Weaver, Zimmerman, and Woosley (1978). It is found that slow proton captures on nuclei with Z between 18 and 25 at temperatures in the range where T9 ranges from 1.25 to 1.7 can reproduce the Ca isotopic anomaly in Allende Ca-Al-rich FUN inclusion EK-1-4-1. It is noted that at T9 = 1.55, the required proton exposure approximately reproduces the Ek-1-4-1 Ti anomaly also. Under these conditions, the production of long-lived Ca-41 and Mn-53, as well as of an anomaly in Cr, is predicted.

  9. Hydrogen burning of the rare oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Buckner, Matthew Quinn

    2014-10-01

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

  10. Isotopic exchange of hydrogen in aromatic amino acids

    SciTech Connect

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

    1993-10-20

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

  11. Sieving hydrogen isotopes through two-dimensional crystals.

    PubMed

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

    2016-01-01

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

  12. Antiphase hydrogen and oxygen isotope periodicity in chert nodules

    NASA Astrophysics Data System (ADS)

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

    2002-09-01

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

  13. Nucleosynthetic W isotope anomalies and the Hf-W chronometry of Ca-Al-rich inclusions

    NASA Astrophysics Data System (ADS)

    Kruijer, Thomas S.; Kleine, Thorsten; Fischer-Gödde, Mario; Burkhardt, Christoph; Wieler, Rainer

    2014-10-01

    Ca-Al-rich inclusions (CAI) are the oldest dated objects formed in the solar system and are pivotal reference points in early solar system chronology. Knowledge of their initial 182Hf/180Hf and 182W/184W is essential, not only for obtaining precise Hf-W ages relative to the start of the solar system, but also to assess the distribution of short-lived radionuclides in the early solar nebula. However, the interpretation of Hf-W data for CAI is complicated by nucleosynthetic W isotope variations. To explore their extent and nature, and to better quantify the initial Hf and W isotope compositions of the solar system, we obtained Hf-W data for several fine- and coarse-grained CAI from three CV3 chondrites. The fine-grained CAI exhibit large and variable anomalies in ε183W (εiW equals 0.01% deviation from terrestrial values), extending to much larger anomalies than previously observed in CAI, and reflecting variable abundances of s- and r-process W isotopes. Conversely, the coarse-grained (mostly type B) inclusions show only small (if any) nucleosynthetic W isotope anomalies. The investigated CAI define a precise correlation between initial ε182W and ε183W, providing a direct empirical means to correct the ε182W of any CAI for nucleosynthetic isotope anomalies using their measured ε183W. After correction for nucleosynthetic W isotope variations, the CAI data define an initial 182Hf/180Hf of (1.018±0.043)×10-4 and an initial ε182W of -3.49±0.07. The Hf-W formation intervals of the angrites D'Orbigny and Sahara 99555 relative to this CAI initial is 4.8±0.6 Ma, in good agreement with Al-Mg ages of these two angrites. This renders a grossly heterogeneous distribution of 26Al in the inner solar system unlikely, at least in the region were CAI and angrites formed.

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

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  16. 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.

  17. Oxygen Isotopic Anomaly in Terrestrial Atmospheric Carbonates and its Implications to Understand the Role of Water on Mars

    NASA Astrophysics Data System (ADS)

    Thiemens, M. H.; Shaheen, R.

    2010-12-01

    Mineral aerosols produced from wind-blown soils are an important component of the earth system and comprise about 1000-3000 Tg.yr-1 compared to 400 Tg.yr-1 of secondary aerosols (e.g. carbonaceous substances, organics, sulfate and nitrates). Aerosols have important consequences for health, visibility and the hydrological cycle as they provide reactive surfaces for heterogeneous chemical transformation that may influence gas phase chemistry in the atmosphere. Tropospheric ozone produced in a cascade of chemical reactions involving NOx and VOC’s, can interact with aerosol surfaces to produce new compounds. Oxygen triple isotopic compositions of atmospheric carbonates have been used for the first time to track heterogeneous chemistry at the aerosol surfaces and to resolve a chemical mechanism that only occurs on particle surfaces. Fine and coarse aerosol samples were collected on filter papers in La Jolla, CA for one week. Aerosol samples were digested with phosphoric acid and released CO2 was purified chromatographically and analyzed for O isotopes after fluorination. Data indicated oxygen isotopic anomaly (Δ17O = δ17O - 0.524 δ18O) ranging from 0.9 to 3.9 per mill. Laboratory experiments revealed that adsorbed water on particle surfaces facilitates the interaction of the gaseous CO2 and O3 with formation of anomalous hydrogen peroxide and carbonates. This newly identified chemical reaction scenario provides a new explanation for production of the isotopically anomalous carbonates found in the SNC Martian meteorites and terrestrial atmospheric carbonates and it also amplifies understanding of water related processes on the surface of Mars. The formation of peroxide via this heterogeneous reaction on aerosols surface suggests a new oxidative process of utility in understanding ozone and oxygen chemistry both at Mars and Earth.

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

    EPA Science Inventory

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

  19. Calcium isotopic anomalies and the lack of aluminum-26 in an unusual Allende inclusion

    NASA Technical Reports Server (NTRS)

    Lee, T.; Russell, W. A.; Wasserburg, G. J.

    1979-01-01

    This letter reports the discovery of an unusual Allende inclusion that is rich in hibonite, Ca(Al, Ti, Mg)12O19, the most refractory and possibly the most primitive major oxide mineral from the solar nebula. The Mg and Ca isotopic compositions of this hibonite-rich inclusion are studied in order to investigate the distribution of Al-26 in the solar system and to extend the search for isotopic anomalies. The Mg results indicate that no Mg isotopic anomalies are present, that the initial Al-26/Al-27 ratio for the inclusion when it crystallized was less than 200 billionths, and that the Mg mass-fractionation effect in the inclusion must be less than about 20 per mil/amu for the hibonite and 10 per mil/amu for other phases. The Ca studies reveal that large Ca mass-fractionation effects of about 7.5 per mil/amu are present and that additional small 'nonlinear' effects of presumably nuclear origin at a level of about 1 to 2 per mil are present in at least Ca-42. A plausible model for the evolution of the hibonite-rich inclusion is outlined.

  20. Cascades for hydrogen isotope separation using metal hydrides

    SciTech Connect

    Hill, F.B.; Grzetic, V.

    1982-01-01

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

  1. 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)

  2. Oxygen Isotope Anomaly in the Carbonate Fractions of Aerosols and its Potential to Assess Urban Pollution

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Abramian, A.; Dominguez, G.; Jackson, T.; Thiemens, M. H.

    2008-12-01

    = 0.887) was observed between oxygen isotope anomaly (Δ17O) in the carbonate fraction of coarse aerosols and urban index, indicating that the isotope anomaly of carbonates can be used as a proxy for urban pollution. Additionally, controlled laboratory experiments to understand the origin of isotope anomaly in the carbonate fraction of aerosols will be discussed.

  3. Isotopic composition of atmospheric hydrogen and methane

    USGS Publications Warehouse

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

    1961-01-01

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

  4. 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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  6. 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.

  7. Hydrogen isotope MicroChemLab FY15.

    SciTech Connect

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

    2015-09-01

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

  8. Hibonite-bearing microspherules - A new type of refractory inclusions with large isotopic anomalies

    NASA Technical Reports Server (NTRS)

    Ireland, T. R.; Fahey, A. J.; Zinner, E. K.

    1991-01-01

    This paper presents petrographic description as well as results on the major- and trace-element chemistry and on Mg, Ca, and Ti isotopic compositions of three refractory inclusions, including 3413-1/31 inclusion from Lance and Murchison 7-228 and 7-753, the mineralogy of which is dominated by the oxide minerals spinel, hibonite, and perovskite. The microspherules examined seem to constitute a separate class of refractory inclusions, characterized by a distinct morphology and mineralogy; large excesses of Ca-48 and Ti-50, and Mg-26 depletions. It is suggested that this type of inclusions must have formed early, prior to the dilution of isotopic anomalies by mixing processes, and in an area characterized by excesses of Ca-48 and Ti-50, depletions of Mg-26, and a lack of Al-26.

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

    SciTech Connect

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1991-03-01

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

  11. Isotopic fractionation during soil uptake of atmospheric hydrogen

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  12. Isotopic fractionation during soil uptake of atmospheric hydrogen

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

  13. The NO+O{sub 3} reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

    SciTech Connect

    Savarino, J.; Morin, S.; Baroni, M.; Bhattacharya, S. K.; Doussin, J.-F.

    2008-05-21

    Atmospheric nitrate shows a large oxygen isotope anomaly ({delta} {sup 17}O), characterized by an excess enrichment of {sup 17}O over {sup 18}O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NO{sub x}=NO+NO{sub 2}). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO{sub x}, greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O{sub 3}. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8{+-}5)%({+-}2{sigma}) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O{sub 3} to NO{sub 2}, which is described by the linear relationship {delta} {sup 17}O(NO{sub 2})=Ax{delta} {sup 17}O(O{sub 3})+B, with A=1.18{+-}0.07({+-}1{sigma}) and B=(6.6{+-}1.5) per mille ({+-}1{sigma}). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

  14. The NO +O3 reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

    NASA Astrophysics Data System (ADS)

    Savarino, J.; Bhattacharya, S. K.; Morin, S.; Baroni, M.; Doussin, J.-F.

    2008-05-01

    Atmospheric nitrate shows a large oxygen isotope anomaly (ΔO17), characterized by an excess enrichment of O17 over O18, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NOx, greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO +O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8±5)%(±2σ) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship ΔO17(NO2)=A ×ΔO17(O3)+B, with A =1.18±0.07(±1σ) and B =(6.6±1.5)‰(±1σ). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

  15. 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.

  16. Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species

    NASA Astrophysics Data System (ADS)

    Morin, S.; Sander, R.; Savarino, J.

    2011-04-01

    The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3-) or hydrogen peroxide (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. This article reviews and illustrates a series of basic concepts relevant to the propagation of the Δ17O of ozone to other reactive or secondary atmospheric species within a photochemical box model. We present results from numerical simulations carried out using the atmospheric chemistry box model CAABA/MECCA to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Using a simplified but realistic tropospheric gas-phase chemistry mechanism, Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the mass-balance equations, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model results confirm that diurnal variations in Δ17O of NOx predicted by the photochemical steady-state relationship during the day match those from the explicit treatment, but not at night. Indeed, the Δ17O of NOx is "frozen" at night as soon as the photolytical lifetime of NOx drops below ca. 10 min. We introduce and quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2, which is of particular relevance to larger-scale simulations of Δ17O where high computational costs cannot be afforded.

  17. 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.

  18. Cerium anomaly across the mid-Tournaisian carbon isotope excursion (TICE)

    NASA Astrophysics Data System (ADS)

    Jiang, G.; Morales, D. C.; Maharjan, D. K.

    2015-12-01

    The Early Mississippian (ca. 359-345 Ma) represents one of the most important greenhouse-icehouse climate transitions in Earth history. Closely associated with this critical transition is a prominent positive carbon isotope excursion (δ13C ≥ +5‰) that has been documented from numerous stratigraphic successions across the globe. This δ13C excursion, informally referred to as the TICE (mid-Tournaisian carbon isotope excursion) event, has been interpreted as resulting from enhanced organic carbon burial, with anticipated outcomes including the lowering of atmospheric CO2 and global cooling, the growth of continental ice sheets and sea-level fall, and the increase of ocean oxygenation and ocean redox changes. The casual relationship between these events has been addressed from various perspectives but not yet clearly demonstrated. To document the potential redox change associated with the perturbation of the carbon cycle, we have analyzed rare earth elements (REE) and trace elements across the TICE in two sections across a shallow-to-deep water transect in the southern Great Basin (Utah and Nevada), USA. In both sections, the REE data show a significant positive cerium (Ce) anomaly (Ce/Ce* = Ce/(0.5La+0.5Pr)). Prior to the positive δ13C shift, most Ce/Ce* values are around 0.3 (between 0.2 and 0.4). Across the δ13C peak, Ce/Ce* values increase up to 0.87, followed by a decrease back to 0.2~0.3 after the δ13C excursion (Figure 1). The positive Ce anomaly is best interpreted as recording expansion of oxygen minimum zone and anoxia resulted from increased primary production. This is consistent with a significant increase of nitrogen isotopes (δ15N) across the δ13C peak. Integration of the carbon, nitrogen, and REE data demonstrates a responsive earth systems change linked to the perturbation of the Early Mississippian carbon cycle.

  19. Heavy-ion isotopic anomalies in He-3 rich solar particle events

    NASA Astrophysics Data System (ADS)

    Mason, G. M.; Mazur, J. E.; Halmilton, D. C.

    1994-04-01

    We have measured the approximately 1 MeV/nucleon heavy-ion mass composition during a series of (3)He-rich solar particle events during 1992 July using the University of Maryland instrument on the SAMPEX spacecraft. In addition to enhancements of He-3/He-4 of approximately 103 to 104 larger than coronal values, these events also showed typical enhancements of heavy nuclei of up to a factor of approximately 10 compared with large solar particle events. Over the energy range of approximately 0.4 - 4.0 MeV/nucleon the spectra of both he isotopes as well as heavier ions C, N, O, Ne, Mg, Si, S, Ca+Ar, and Fe were found to be power laws in enegy per nucleon with nearly identical spectral indices, indicating that both the He and heavier ions were accelerated by the same mechanism. We obtain upper limits of approximately 15 for possible enrichments of neutron-rich isotopes of C, N, O, and Fe compared to large solar particle events; however, we find Ne-22/Ne-20 = 0.29 +/- 0.10, an enhancement of a factor of 3-4 compared with large solar particle event abundances. We also find evidence of enrichments of approximately 2-3 for Mg-25/Mg-24 and Mg-26/Mg-24, although the uncertainties are large. Thus while at least one of the heavy elements shows isotopic enhancements of neutron-rich isotopes, the mechanisms that produce the extremely large He-3 enrichments apparently do not produce similarly dramatic isotopic anomalies in the heavy nuclei. These observations constrain possible acceleration models and may indicate that the particles are energized in solar coronal locations enhanced in heavy ions.

  20. Heavy hydrogen isotopes penetration through austenitic and martensitic steels

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

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

  1. 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

  2. Calculation of hydrogen isotopic fractionations in biogeochemical systems

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Hayes, John M.

    2005-02-01

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

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

    SciTech Connect

    Butler, J.P.

    1980-04-01

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

  4. Large isotopic anomalies of Si, C, N and noble gases in interstellar silicon carbide from the Murray meteorite

    NASA Astrophysics Data System (ADS)

    Zinner, E.; Ming, T.; Anders, E.

    1987-12-01

    Primitive meteorites contain several noble gas components with anomalous isotopic compositions which imply that they - and their solid 'carrier' phases - are of exotic, pre-solar origin. The authors found that minor fractions of the Murray meteorite contain two minerals not previously seen in meteorites: silicon carbide and an amorphous Si-O phase. They report ion microprobe analyses of these phases which reveal very large isotopic anomalies in silicon, nitrogen and carbon, exceeding the highest anomalies previously measured by factors of up to ≡50. It is concluded that these phases are circumstellar grains from carbon-rich stars, whose chemical inertness allowed them to survive in exceptionally well-preserved form.

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

    SciTech Connect

    Xiao, S.; Heung, L.

    2010-10-07

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

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

    SciTech Connect

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

    1999-07-10

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  8. Unexpected hydrogen isotope variation in oceanic pelagic seabirds.

    PubMed

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

    2014-08-01

    Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142‰ range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology. PMID:24989118

  9. The hydrogen anomaly in neutron Compton scattering: new experiments and a quantitative theoretical explanation

    NASA Astrophysics Data System (ADS)

    Karlsson, E. B.; Hartmann, O.; Chatzidimitriou-Dreismann, C. A.; Abdul-Redah, T.

    2016-08-01

    No consensus has been reached so far about the hydrogen anomaly problem in Compton scattering of neutrons, although strongly reduced H cross-sections were first reported almost 20 years ago. Over the years, this phenomenon has been observed in many different hydrogen-containing materials. Here, we use yttrium hydrides as test objects, YH2, YH3, YD2 and YD3, Y(H x D1‑x )2 and Y(H x D1‑x )3, for which we observe H anomalies increasing with transferred momentum q. We also observe reduced deuteron cross-sections in YD2 and YD3 and have followed those up to scattering angles of 140° corresponding to high momentum transfers. In addition to data taken using the standard Au-197 foils for neutron energy selection, the present work includes experiments with Rh-103 foils and comparisons were also made with data from different detector setups. The H and D anomalies are discussed in terms of the different models proposed for their interpretation. The ‘electron loss model’ (which assumes energy transfer to excited electrons) is contradicted by the present data, but it is shown here that exchange effects in scattering from two or more protons (or deuterons) in the presence of large zero-point vibrations, can explain quantitatively the reduction of the cross-sections as well as their q-dependence. Decoherence processes also play an essential role. In a scattering time representation, shake-up processes can be followed on the attosecond scale. The theory also shows that large anomalies can appear only when the neutron coherence lengths (determined by energy selection and detector geometry) are about the same size as the distance between the scatterers.

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

    NASA Astrophysics Data System (ADS)

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

    2004-04-01

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

  11. 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.

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

    SciTech Connect

    Jewett, J.R., Fluor Daniel Hanford

    1997-02-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Hu, Alice; Hassanein, Ahmed

    2014-03-01

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

  15. Ca ISOTOPE EFFECTS IN ORGUEIL LEACHATES AND THE IMPLICATIONS FOR THE CARRIER PHASES OF {sup 54}Cr ANOMALIES

    SciTech Connect

    Moynier, Frederic; Podosek, Frank A.; Brannon, Joyce; Simon, Justin I.; DePaolo, Donald J.; Meyer, Bradley S. E-mail: fap@levee.wustl.ed E-mail: Justin.I.Simon@NASA.go E-mail: mbradle@clemson.ed

    2010-07-20

    Primitive meteorites contain small {sup 40}Ca excesses, in addition to rare anomalies in {sup 48}Ca. Refractory inclusions from Vigarano and Allende have larger {sup 40}Ca and resolvable {sup 48}Ca anomalies. These results imply that Ca isotopic heterogeneities were still present in the early solar system at both the mineral and whole-rock scale. The absence of correlated Ca isotope anomalies in leachates from the CI1 chondrite Orgueil containing large {sup 54}Cr anomalies has implications on the origin of the Cr anomalies. {sup 54}Cr has to be produced either in massive stars during s-process nucleosynthesis without accompanying {sup 48}Ca or in particular zones in the rare Type Ia supernovae. In the latter case, {sup 54}Cr has been produced in a zone predominantly enriched in Cr and {sup 54}Cr and not mixed with other zones, or {sup 54}Cr has been produced together with other neutron-rich nuclides and there has been subsequent decoupling of this material in the star, in the solar system, or in the laboratory.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  17. Erosion during accretion: Consequences for planetary iron-silicate ratios and tungsten isotope anomalies

    NASA Astrophysics Data System (ADS)

    Dwyer, C. A.; Nimmo, F.; Asphaug, E. I.; O'Brien, D. P.; Chambers, J.

    2011-12-01

    The late stages of planetary accretion involve stochastic, large collisions [1]. Although such collisions are usually assumed to result in perfect mergers, many of the collisions may instead result in hit-and-run events [2, 3] or erosion of existing bodies' mantles [4]. Impact-related erosion can have profound consequences for the rate and style of accretion [5] and the bulk chemistries of terrestrial planets [6]. Here we present some preliminary investigations into the occurrence of erosional collisions during late-stage accretion and consequences for the bulk chemistry and isotopic characteristics of the resulting planets. We have performed a preliminary investigation into the nature of late-stage accretion using an N-body simulation in which the different possible collision outcomes are treated in a more realistic manner than hitherto. The simulation starts with 155 planetesimals of roughly lunar mass; at the end, four bodies remain with masses of 0.83, 0.62, 0.33, and 0.02 Mearth. Collisional efficiency is parametrized based on the results of [7]. The results of the collisions, especially highly disruptive collisions, are idealized in order to be computationally tractable; in particular, bodies smaller than a minimum mass are not permitted. To track the bulk compositional evolution of the bodies, we assume all are initially chondritic. We alter the bulk chemistry after an impact according to a scheme which is based on the assumption that mantle material is much more likely to be eroded than core material. We track the tungsten isotopic evolution of each body using the method of [8] and treat the extent of core-mantle equilibration as a free parameter. The stochastic nature of planetary accretion means that even with perfect mergers, the tungsten isotope anomaly (eW) of the final bodies will vary, due to variations in the timing of the impacts which create the final bodies. Irrespective of accretion style, the extent of core re-equilibration affects e

  18. Delineating the effect of El-Nino Southern Oscillations using oxygen and sulfur isotope anomalies of sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Abaunza Quintero, M. M.; Jackson, T.; McCabe, J.; Savarino, J. P.; Thiemens, M. H.

    2013-12-01

    Sulfate aerosols, unlike greenhouse gases, contribute to global cooling by acting as cloud condensation nuclei in the troposphere and by directly reflecting solar radiation in the stratosphere. To understand the long-term effect of natural and anthropogenic sulfate aerosol on the climate cycle, it is critical to obtain a clear picture of the factors controlling the transport and transformation of sulfate aerosols. We have employed both oxygen triple isotopes and sulfur quadruple isotopes on sulfates from Antarctic ice samples to define the oxidation history, long range transport dynamics, and sources of sulfate aerosols over time. The measurements are used to deconvolve the impact of natural and anthropogenic aerosols on the stratospheric sulfate aerosol composition. Sulfate aerosols were extracted from a snow pit at the South Pole (1979-2002) with a high resolution temporal (6 month) record of the winter and summer seasons covering two largest volcanic events, Pinatubo and El-chichon and three largest ENSO events of the century. All three oxygen and four sulfur isotopes were measured on the extracted sulfate (Shaheen et al., 2013). The high temperature pyrolysis (1000oC) of silver sulfate yielded O2 and SO2. The oxygen triple isotopic composition of the O2 gas was used to determine the oxidation history of sulfate aerosol and SO2 gas obtained during this reaction was utilized to measure sulfur quadruple isotopes following appropriate reaction chemistry (Farquhar et al., 2001). The data revealed that oxygen isotope anomalies in Antarctic aerosols (Δ17O = 0.8-3.7‰) from 1990 to 2001 are strongly linked to the variation in ozone levels in the upper stratosphere/lower stratosphere. The variations in ozone levels are reflective of the intensity of the ENSO events and changes in relative humidity in the atmosphere during this time period. Sulfate concentrations and sulfur quadruple isotopic composition and associated anomalies were used to elucidate the sources of

  19. Intracrystalline site preference of hydrogen isotopes in borax

    SciTech Connect

    Pradhananga, T.M.; Matsuo, S.

    1985-01-03

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

  20. Hydrogen isotope exchange experiments with Mt Mazama ash

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  1. 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.

  2. Surface studies of metals after interaction with hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Silver, David Samuel

    1998-12-01

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

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

    PubMed

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

    2016-08-19

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H_{2}/D_{2} gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation. PMID:27588855

  4. NEST-GENERATION TCAP HYDROGEN ISOTOPE SEPARATION PROCESS

    SciTech Connect

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

    2007-08-07

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

  5. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  6. Retention of Hydrogen Isotopes in Neutron Irradiated Tungsten

    SciTech Connect

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

    2013-03-01

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

  7. Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

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

  8. Carbon isotope curve and iridium anomaly in the Albian-Cenomanian paleoceanic deposits of the Eastern Kamchatka

    NASA Astrophysics Data System (ADS)

    Savelyev, D. P.; Savelyeva, O. L.; Palechek, T. N.; Pokrovsky, B. G.

    2012-04-01

    determined contents of carbon and oxygen stable isotopes in limestones and have compared the received results to isotope curves of other regions. In studied section the curve of d13C is characterized by a clearly expressed positive shift at the level of the lower carbonaceous bed. Below it and in the overlapping stratum of siliceous limestone (1 cm thickness) d13C has the values of 1.9-2.1 pro mille and above it d13C increases up to 2.5-3 pro mille. The precise d13C maximum after a sharp shift is correlatable with the form of a d13C curve of the Middle Cenomanian Tethyan sections. Accordingly, it is possible to assert, that the lower carbonaceous bed was formed during the mid-Cenomanian anoxic event (MCE). Gradual increase of d13C in the upper part of our section is similar to change of d13C in Upper Cenomanian fragments of Tethyan sections, i.e. the lower carbonaceous bed corresponds to anoxic event at the Cenomanian/Turonian boundary (OAE2). Neutron activation analysis indicates increased up to 9 ppb concentration of Ir at the bottom of the lower carbonaceous bed (inorganic part of the sample was analyzed comprising 46% of the bulk rock). This anomaly correlates in the studied section with a positive shift of d13C. Taking into account radiolarian age data this allows to correlate the anomaly with the MCE. A source of iridium and other elements of the platinum group could be basalts and hyaloclastites from the eruptions during the sedimentation period. Anoxic conditions promoted deposit enrichment in ore elements. This work was supported by the RFBR (No. 10-05-00065).

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  10. O-16 excesses in Murchison and Murray hibonites - A case against a late supernova injection origin of isotopic anomalies in O, Mg, Ca, and Ti

    NASA Technical Reports Server (NTRS)

    Fahey, A. J.; Goswami, J. N.; Mckeegan, K. D.; Zinner, E. K.

    1987-01-01

    Ion probe measurements of the oxygen isotopic composition of seven hibonite samples from the CM chondrites Murchison and Murray are reported. All samples show large O-16 excesses relative to terrestrial oxygen. The data for all samples plot along the carbonaceous chondrite O-16-rich mixing line and show no evidence for isotopic mass fractionation effects characteristic of FUN inclusions. These hibonites have the largest Ca-48 and Ti-50 isotopic anomalies found to date; thus there is no intrinsic relationship between anomalies of a nucleosynthetic origin and isotopic mass fractionation effects. The large O-16 excess seen in the sample with the largest measured Ca-48 and Ti-50 depletions argues against a late injection of exotic material from a nearby supernova as a source for the isotopic anomalies.

  11. Isotope Effects in Collisional VT Relaxation of Molecular Hydrogen

    NASA Technical Reports Server (NTRS)

    Bieniek, R. J.

    2006-01-01

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

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

    SciTech Connect

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

    2003-06-01

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

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

    SciTech Connect

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

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

  14. 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

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

    PubMed

    Wang, Shi-xia; Zheng, Hai-fei

    2011-03-01

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

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

    SciTech Connect

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

    2008-07-15

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

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

    SciTech Connect

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

    2008-07-15

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

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

    PubMed

    Bidica, Nicolae

    2012-01-01

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

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

    SciTech Connect

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

    1993-07-01

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

  20. Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

    NASA Technical Reports Server (NTRS)

    Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milam, Stefanie N.

    2012-01-01

    Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

  1. ISOTOPIC ANOMALIES IN PRIMITIVE SOLAR SYSTEM MATTER: SPIN-STATE-DEPENDENT FRACTIONATION OF NITROGEN AND DEUTERIUM IN INTERSTELLAR CLOUDS

    SciTech Connect

    Wirstroem, Eva S.; Cordiner, Martin A.; Charnley, Steven B.; Milam, Stefanie N.

    2012-09-20

    Organic material found in meteorites and interplanetary dust particles is enriched in D and {sup 15}N. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and {sup 15}N and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large {sup 15}N enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, {sup 15}N enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H{sub 2}, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both {sup 15}N and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest {sup 15}N enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system {sup 15}N and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

  2. Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

    NASA Technical Reports Server (NTRS)

    Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milan, Stefanie N.

    2012-01-01

    Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

  3. 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.

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

    SciTech Connect

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

    2005-07-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Isotopic anomaly in peat nitrogen is a probable trace of acid rains caused by 1908 Tunguska bolide

    NASA Astrophysics Data System (ADS)

    Kolesnikov, E. M.; Kolesnikova, N. V.; Boettger, T.

    1998-02-01

    In peat sampled at the Tunguska Cosmic Body (TCB) explosion area, the sharp increase of the N concentration (about three-fold) and the positive N isotopic anomaly (δ 15N = + 3.5‰, see eqn) have for the first time been revealed. In contrast with the C and H effects observed earlier which were clearly limited to the epicentre area (Kolesnikov et al., 1997 in press), the same N effect has also been shown in peat sampled near the Vanavara settlement, 65 km south of the explosion epicentre. A clear connection of the observed anomalies in peat to the 1908 permafrost boundary, synchronism of the changes of δ 15N and the N concentration and also good agreement with data on the K/T boundary deposits allow us to connect the observed effects to acid rain fall-out after passage and an explosion of the TCB.

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    SciTech Connect

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  10. Hydrogen isotope trapping in Al-Cu binary alloys

    DOE PAGESBeta

    Chao, Paul; Karnesky, Richard A.

    2016-01-01

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

  11. 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.

  12. Hydrogen isotope trapping in Al-Cu binary alloys

    SciTech Connect

    Chao, Paul; Karnesky, Richard A.

    2016-01-01

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

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

    SciTech Connect

    Bystritskii, V.M.

    1995-05-01

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

  14. Zinc isotopic composition of iron meteorites: Absence of isotopic anomalies and origin of the volatile element depletion

    NASA Astrophysics Data System (ADS)

    Chen, Heng; Nguyen, Bach Mai; Moynier, Frédéric

    2013-12-01

    High-precision Zn isotopic compositions measured by MC-ICP-MS are documented for 32 iron meteorites from various fractionally crystallized and silicate-bearing groups. The δ66Zn values range from -0.59‰ up to +5.61‰ with most samples being slightly enriched in the heavier isotopes compared with carbonaceous chondrites (0 < δ66Zn < 0.5). The δ66Zn versus δ68Zn plot of all samples defines a common linear fractionation line, which supports the hypothesis that Zn was derived from a single reservoir or from multiple reservoirs linked by mass-dependent fractionation processes. Our data for Redfields fall on a mass fractionation line and therefore refute a previous claim of it having an anomalous isotopic composition due to nonmixing of nucleosynthetic products. The negative correlation between δ66Zn and the Zn concentration of IAB and IIE is consistent with mass-dependent isotopic fractionation due to evaporation with preferential loss of lighter isotopes in the vapor phase. Data for the Zn concentrations and isotopic compositions of two IVA samples demonstrate that volatile depletion in the IVA parent body is not likely the result of evaporation. This is important evidence that favors the incomplete condensation origin for the volatile depletion of the IVA parent body.

  15. 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.

  16. NUCLEOSYNTHETIC TUNGSTEN ISOTOPE ANOMALIES IN ACID LEACHATES OF THE MURCHISON CHONDRITE: IMPLICATIONS FOR HAFNIUM-TUNGSTEN CHRONOMETRY

    SciTech Connect

    Burkhardt, Christoph; Wieler, Rainer; Kleine, Thorsten; Dauphas, Nicolas

    2012-07-01

    Progressive dissolution of the Murchison carbonaceous chondrite with acids of increasing strengths reveals large internal W isotope variations that reflect a heterogeneous distribution of s- and r-process W isotopes among the components of primitive chondrites. At least two distinct carriers of nucleosynthetic W isotope anomalies must be present, which were produced in different nucleosynthetic environments. The co-variation of {sup 182}W/{sup 184}W and {sup 183}W/{sup 184}W in the leachates follows a linear trend that is consistent with a mixing line between terrestrial W and a presumed s-process-enriched component. The composition of the s-enriched component agrees reasonably well with that predicted by the stellar model of s-process nucleosynthesis. The co-variation of {sup 182}W/{sup 184}W and {sup 183}W/{sup 184}W in the leachates provides a means for correcting the measured {sup 182}W/{sup 184}W and {sup 182}W/{sup 183}W of Ca-Al-rich inclusions (CAI) for nucleosynthetic anomalies using the isotopic variations in {sup 183}W/{sup 184}W. This new correction procedure is different from that used previously, and results in a downward shift of the initial {epsilon}{sup 182}W of CAI to -3.51 {+-} 0.10 (where {epsilon}{sup 182}W is the variation in 0.01% of the {sup 182}W/{sup 183}W ratio relative to Earth's mantle). This revision leads to Hf-W model ages of core formation in iron meteorite parent bodies that are {approx}2 Myr younger than previously calculated. The revised Hf-W model ages are consistent with CAI being the oldest solids formed in the solar system, and indicate that core formation in some planetesimals occurred within {approx}2 Myr of the beginning of the solar system.

  17. 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.

  18. 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

  19. 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.

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

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2010-09-15

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ(2)H reproducibility (1σ standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN(2) is used as a moisture trap for gaseous hydrogen. PMID:20718408

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  3. DUPAL anomaly in the Sea of Japan: Pb, Nd, and Sr isotopic variations at the eastern Eurasian continental margin

    USGS Publications Warehouse

    Tatsumoto, M.; Nakamura, Y.

    1991-01-01

    Volcanic rocks from the eastern Eurasian plate margin (southwestern Japan, the Sea of Japan, and northeastern China) show enriched (EMI) component signatures. Volcanic rocks from the Ulreung and Dog Islands in the Sea of Japan show typical DUPAL anomaly characteristics with extremely high ??208/204 Pb (up to 143) and enriched Nd and Sr isotopic compositions (??{lunate}Nd = -3 to -5, 87Sr 86Sr = ~0.705). The ??208/204 Pb values are similar to those associated with the DUPAL anomaly (up to 140) in the southern hemisphere. Because the EMI characteristics of basalts from the Sea of Japan are more extreme than those of southwestern Japan and inland China basalts, we propose that old mantle lithosphere was metasomatized early (prior to the Proterozoic) with subduction-related fluids (not present subduction system) so that it has been slightly enriched in incompatible elements and has had a high Th/U for a long time. The results of this study support the idea that the old subcontinental mantle lithosphere is the source for EMI of oceanic basalts, and that EMI does not need to be stored at the core/ mantle boundary layer for a long time. Dredged samples from seamounts and knolls from the Yamato Basin Ridge in the Sea of Japan show similar isotopic characteristics to basalts from the Mariana arc, supporting the idea that the Yamato Basin Ridge is a spreading center causing separation of the northeast Japan Arc from Eurasia. ?? 1991.

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

    NASA Astrophysics Data System (ADS)

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

    2008-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-08-01

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

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

    PubMed

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

    2016-03-15

    Aerobic and anaerobic polycyclic aromatic hydrocarbon (PAH) biodegradation was characterized by compound specific stable isotope analysis (CSIA) of the carbon and hydrogen isotope effects of the enzymatic reactions initiating specific degradation pathways, using naphthalene and 2-methylnaphtalene as model compounds. Aerobic activation of naphthalene and 2-methylnaphthalene by Pseudomonas putida NCIB 9816 and Pseudomonas fluorescens ATCC 17483 containing naphthalene dioxygenases was associated with moderate carbon isotope fractionation (εC = -0.8 ± 0.1‰ to -1.6 ± 0.2‰). In contrast, anaerobic activation of naphthalene by a carboxylation-like mechanism by strain NaphS6 was linked to negligible carbon isotope fractionation (εC = -0.2 ± 0.2‰ to -0.4 ± 0.3‰). Notably, anaerobic activation of naphthalene by strain NaphS6 exhibited a normal hydrogen isotope fractionation (εH = -11 ± 2‰ to -47 ± 4‰), whereas an inverse hydrogen isotope fractionation was observed for the aerobic strains (εH = +15 ± 2‰ to +71 ± 6‰). Additionally, isotope fractionation of NaphS6 was determined in an overlaying hydrophobic carrier phase, resulting in more reliable enrichment factors compared to immobilizing the PAHs on the bottle walls without carrier phase. The observed differences especially in hydrogen fractionation might be used to differentiate between aerobic and anaerobic naphthalene and 2-methylnaphthalene biodegradation pathways at PAH-contaminated field sites. PMID:26855125

  9. 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.

  10. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis

    PubMed Central

    Chakraborty, Subrata; Jackson, Teresa L.; Ahmed, Musahid; Thiemens, Mark H.

    2013-01-01

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models. PMID:23431159

  11. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis.

    PubMed

    Chakraborty, Subrata; Jackson, Teresa L; Ahmed, Musahid; Thiemens, Mark H

    2013-10-29

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models. PMID:23431159

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

    PubMed

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

    2013-06-01

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

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

    SciTech Connect

    DeNiro, M.J.; Epstein, S.

    1981-12-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  15. 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.

  16. American woodcock migratory connectivity as indicated by hydrogen isotopes

    USGS Publications Warehouse

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Schwab, Valérie F.; Sachs, Julian P.

    2011-12-01

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

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

    PubMed

    Lyons, J R; Young, E D

    2005-05-19

    The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO. PMID:15902251

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

    NASA Astrophysics Data System (ADS)

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

    2002-11-01

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

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

    SciTech Connect

    Melius, C F; Foltz, G W

    1987-01-01

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

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

    PubMed

    Koehler, Geoff; Wassenaar, Leonard I

    2012-04-17

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

  2. 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.

  3. 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.

  4. Carbon and hydrogen isotopic composition of bacterial methane in a shallow freshwater lake

    SciTech Connect

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

    1984-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  6. 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

  7. 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. "

  8. 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.

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

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-03-01

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

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

    SciTech Connect

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    A selected bibliography on heavy water, tritiated water and hydrogen isotopes is presented. This bibliography covers the period 1981-1992 and is in continuation to Division's earlier report BARC-1192 (1983). The sources of information for this compilation are Chemical Abstracts, INIS Atom Index and also some scattered search through journals and reports available in our library. No claim is made towards exhaustiveness of this bibliography even though sincere attempts have been made for a wide coverage. The bibliography is arranged under the headings: (1) production, purification, recovery, reprocessing and storage; (2) isotope exchange; (3) isotope analysis; (4) properties; and (5) miscellaneous. Total number of references in the bibliography are 1762.

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

    USGS Publications Warehouse

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

    1973-01-01

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

  13. Tales of volcanoes and El-Niño southern oscillations with the oxygen isotope anomaly of sulfate aerosol

    PubMed Central

    Shaheen, Robina; Abauanza, Mariana; Jackson, Teresa L.; McCabe, Justin; Savarino, Joel; Thiemens, Mark H.

    2013-01-01

    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth’s system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980–2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher ∆17O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and ∆17O = 3.3‰, OEI = 11 and ∆17O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that ∆17O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations. PMID:23447567

  14. Tales of volcanoes and El-Nino southern oscillations with the oxygen isotope anomaly of sulfate aerosol.

    PubMed

    Shaheen, Robina; Abauanza, Mariana; Jackson, Teresa L; McCabe, Justin; Savarino, Joel; Thiemens, Mark H

    2013-10-29

    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher (17)O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and (17)O = 3.3‰, OEI = 11 and (17)O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that (17)O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations. PMID:23447567

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

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

    PubMed

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

    2003-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

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

    PubMed

    Macrae, Roderick M

    2013-01-01

    Hydrogen has a central role in the story of the universe itself and also in the story of our efforts to understand it. This paper retells the story of the part played by hydrogen and its stable isotope deuterium in the primordial synthesis of the elements, then goes on to describe how the spectrum of atomic hydrogen led to insights into the laws governing matter at the most fundamental level, from the quantum mechanics of Schrödinger and Heisenberg, through quantum electrodynamics, to the most recent work investigating the underlying structure of the proton itself. Atomic hydrogen is unique among the elements in that the concept of isotopy--atoms having the same nuclear charge but different masses--is stretched to its limit in the isotopes of hydrogen, ranging from the well-known isotopes deuterium and tritium to exotic species such as muonium, muonic helium, and positronium. These atoms, or atom-like objects, have much to tell us about fundamental aspects of the universe. In recent years the idea of utilizing hydrogen either as an energy source (through nuclear fusion) or as an energy storage medium (bound in hydrides or other materials) has attracted much attention as a possible avenue to a post-oil energy future. Some of the more interesting recent developments are described here. Dedicated to the memory of Brian C. Webster (1939-2008). PMID:24244971

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by us and others as intermediary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II° quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample. Samples of carboxylic acid (C1 through C4) and alcohols (C1 through C4) were pyrolyzed at 200°C on a CDS Analytical. Inc. Model 5200° pyroprobe and passed through a Thermo Electron GC-MS-TC-IRMS system operating in continuous flow mode. The High Temperature Conversion step

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

    PubMed

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

    2002-03-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  2. 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.

  3. 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

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

    PubMed

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

    2013-12-01

    Chloromethane (CH3 Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (ε) of -29‰ and -27‰ for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in (13) C of untransformed CH3 Cl was also observed, and similar isotope enrichment factors (ε) of -41‰ and -38‰ were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane. PMID:24019296

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

    SciTech Connect

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

    2008-02-25

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

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

    PubMed

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

    2014-10-28

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

  7. 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)

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

    NASA Astrophysics Data System (ADS)

    Marumo, Katsumi; Nagasawa, Keinosuke; Kuroda, Yoshimasu

    1980-04-01

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

  9. Isotope systematics of Li, Sr, Nd, and volatiles in Indian Ocean MORBs of the Rodrigues Triple Junction: Constraints on the origin of the DUPAL anomaly

    NASA Astrophysics Data System (ADS)

    Nishio, Yoshiro; Nakai, Shun'ichi; Ishii, Teruaki; Sano, Yuji

    2007-02-01

    The DUPAL anomaly, a radiogenic isotope anomaly discovered in the Indian Ocean mantle, has been interpreted as due to a large-scale mantle heterogeneity. To provide new constraints on the DUPAL origin, we analyzed isotope ratios of Li, Sr, and Nd in fresh N-MORB glasses recovered from the Rodrigues Triple Junction in the Indian Ocean, and from the North Atlantic. The Li isotopic compositions of the Indian Ocean DUPAL N-MORBs were comparable to those of the North Atlantic non-DUPAL N-MORBs. The source of the DUPAL signature in Indian Ocean MORBs and the E-MORB-type enriched mantle source have quite different Li isotopic compositions. The 143Nd/ 144Nd values of both sources are significantly lower than those of the North Atlantic N-MORBs. The δ 7Li values of most oceanic island basalts with similar low 143Nd/ 144Nd signatures are also higher than those of the North Atlantic N-MORBs, except for several Koolau lavas. The Li isotope results support the recent proposal that significant amounts of recycled lower continental crust might produce the radiogenic isotope signatures of the Indian Ocean DUPAL source.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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