Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

Science.gov (United States)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Experimental investigation of H2/D2 isotope separation by cryo-adsorption in metal-organic frameworks

International Nuclear Information System (INIS)

Teufel, Julia Sonja

2012-01-01

Light-gas isotopes differ in their adsorption behavior under cryogenic conditions in nanoporous materials due to their difference in zero-point energy. However, the applicability of these cryo-effects for the separation of isotope mixtures is still lacking an experimental proof. The current work describes the first experimentally obtained H 2 /D 2 selectivity values of nanoporous materials measured by applying isotope mixtures in low-temperature thermal desorption spectroscopy (TDS). The dissertation contains the following key points: 1) A proof of the experimental method, i.e. it is shown that TDS leads to reasonable selectivity values. 2) A series of small-pore MFU-4 derivatives (MOFs) is shown to separate isotope mixtures by quantum sieving, i.e. by the difference in the adsorption kinetics. The influence of the pore size on the selectivity is studied systematically for this series. 3) Two MOFs with pores much larger than the kinetic diameter of H 2 do not exhibit kinetic quantum sieving. However, if the MOFs are exposed to an isotope mixture, deuterium adsorbs preferentially at the adsorption sites with high heats of adsorption. According to the experimental results, these strong adsorption sites can be every selective for deuterium. On the basis of the experimentally obtained selectivity values, technical implementations for H 2 /D 2 light-gas isotope separation by cryo-adsorption are described.

Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

International Nuclear Information System (INIS)

Marx, D.

1959-11-01

We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

18O, 2H and 3H isotopic composition of precipitation and shallow groundwater in Olkiluoto

International Nuclear Information System (INIS)

Hendriksson, N.; Karhu, J.; Niinikoski, P.

2014-12-01

The isotopic composition of oxygen and hydrogen in local precipitation is a key parameter in the modelling of local water circulation. This study was initiated in order to provide systematic monthly records of the isotope content of atmospheric precipitation in the Olkiluoto area and to establish the relation between local rainfall and newly formed groundwater. During January 2005 - December 2012, a total of 85 cumulative monthly rainfall samples and 68 shallow groundwater samples were collected and the isotopic composition of oxygen and hydrogen was recorded for all those samples. Tritium values are available for 79 precipitation and 65 groundwater samples. Based on the 8-year monitoring, the long-term weighted annual mean isotope values of precipitation and the mean values of shallow groundwater are -11.59 per mille and -11.27 per mille for δ 18 O, - 82.3 per mille and -80.3 per mille for δ 2 H and 9.8 and 9.1 TU for tritium, respectively. Based on these data, the mean stable isotope ratios of groundwater represent the long-term mean annual isotopic composition of local precipitation. The precipitation data were used to establish the local meteoric water line (LMWL) for the Olkiluoto area. The line is formulated as: δ 2 H = 7.45 star δ 18 O + 3.82. The isotope time series reveal a change in time. The increasing trend for the δ 18 O and δ 2 H values may be related to climatic variability while the gradual decline observed in the 3 H data is attributed to the still continuing decrease in atmospheric 3 H activity in the northern hemisphere. The systematic seasonal and long-term tritium trends suggest that any potential ground-level tritium release from the Olkiluoto nuclear power plants is insignificant. The d-excess values of Olkiluoto precipitation during the summer period indicated that a notable amount of re-cycled Baltic Sea water may have contributed to precipitation in the Finnish southern coast. Preliminary estimates of the evaporated Baltic Sea water

2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

Science.gov (United States)

Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

2010-05-01

Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

Science.gov (United States)

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

International Nuclear Information System (INIS)

Kellner, C.S.; Bell, A.T.

1981-01-01

The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

The H{sup +}{sub 3} + H{sub 2} isotopic system. Origin of deuterium astrochemistry

Energy Technology Data Exchange (ETDEWEB)

Hugo, Edouard Jean-Marie

2008-07-01

Dense cold molecular clouds reckoned to be stellar nurseries are the scene of an extreme molecular deuteration. Despite the cosmic D/H ratio of {proportional_to}10{sup -5}, molecular species in prestellar cores are observed to contain nearly as much deuterium as hydrogen. This astonishing deuterium enrichment promoted by low temperatures is the work of H{sup +}{sub 3}. It is the key species which unlocks the deuterium from its HD reservoir via reactions like H{sup +}{sub 3}+HD {r_reversible} H{sub 2}D{sup +}+H{sub 2} and drags it further to other species in successive reactions. For this reason, the H{sup +}{sub 3}+H{sub 2} isotopic system is outstandingly critical for the astrochemistry of cold environments. However, its understanding is yet incomplete and insufficient. This thesis thus focuses on the H{sup +}{sub 3}+H{sub 2} isotopic system from a theoretical, experimental and astronomical point of view giving a particular look into the role of nuclear spins. As a first step, the stringent nuclear spin selection rules in associative, dissociative and reactive collisions are investigated. This purely theoretical study zooms into the details of the nuclear spin wavefunctions and shows that their permutation symmetry representation is necessary and sufficient, contrary to their angular momentum representation. Additionally, a new deterministic interpretation of nuclear spins in chemical reactions is proposed. Based on these considerations, a complete set of state-to-state rate coefficients for all H{sup +}{sub 3} + H{sub 2} isotopic variants is calculated using a microcanonical model leaned on phase space theory. An experimental study is conducted in parallel with a 22-pole ion trap apparatus in order to inspect the influences of temperature and H{sub 2} ortho-to-para ratio. The good overall agreement between experimental and theoretical results supports the validity and utility of the calculated set of rate coefficients. Furthermore, the potentiality of the 22-pole

Hydration of DNA by tritiated water and isotope distribution: a study by 1H, 2H, and 3H NMR spectroscopy

International Nuclear Information System (INIS)

Mathur-De Vre, R.; Grimee-Declerck, R.; Lejeune, P.; Bertinchamps, A.J.

1982-01-01

The hydration layer of DNA (0.75%) in tritiated water represents 3.5% of solvent 3 HHO. The combined effects of temperature (-6 to -40 0 C) and H 2 O/ 2 H 2 O solvent composition on the spin-lattice relaxation times of water protons and deuterons suggest selective distribution of isotopes in the hydration layer. The ''hydration isotope'' effect and the localization of tritiated water molecules in the hydration layer of DNA have important implications in describing the radiobiological effects of tritiated water because the initial molecular damage caused by 3 HHO (internal radiation source) localizes close to 3 H due to the short range and low energy of 3 H β rays

Process for the production of heavy water by H2-methylamine isotopic exchange

International Nuclear Information System (INIS)

Briec, M.; Ravoire, J.; Rostaing, M.

1977-01-01

An isotopic exchange process for separating D 2 from H 2 is presented. The H 2 -monomethylamine system is studied on the laboratory scale (kinetics, H 2 solubility, thermal stability and solubility of the catalyst) and on the pilot plant scale (operating conditions and economics) [fr

Analysis of stable isotope ratios (δ18O and δ2H) in precipitation of the Verde River watershed, Arizona 2003 through 2014

Science.gov (United States)

Beisner, Kimberly R.; Paretti, Nicholas V.; Tucci, Rachel S.

2016-04-25

Stable isotope delta values (δ18O and δ2H) of precipitation can vary with elevation, and quantification of the precipitation elevation gradient can be used to predict recharge elevation within a watershed. Precipitation samples were analyzed for stable isotope delta values between 2003 and 2014 from the Verde River watershed of north-central Arizona. Results indicate a significant decrease in summer isotopic values overtime at 3,100-, 4,100-, 6,100-, 7,100-, and 8,100-feet elevation. The updated local meteoric water line for the area is δ2H = 7.11 δ18O + 3.40. Equations to predict stable isotopic values based on elevation were updated from previous publications in Blasch and others (2006), Blasch and Bryson (2007), and Bryson and others (2007). New equations were separated for samples from the Camp Verde to Flagstaff transect and the Prescott to Chino Valley transect. For the Camp Verde to Flagstaff transect, the new equations for winter precipitation are δ18O = -0.0004z − 8.87 and δ2H = -0.0029z − 59.8 (where z represents elevation in feet) and the summer precipitation equations were not statistically significant. For the Prescott to Chino Valley transect, the new equations for summer precipitation are δ18O = -0.0005z − 3.22 and δ2H = -0.0022z − 27.9; the winter precipitation equations were not statistically significant and, notably, stable isotope values were similar across all elevations. Interpretation of elevation of recharge contributing to surface and groundwaters in the Verde River watershed using the updated equations for the Camp Verde to Flagstaff transect will give lower elevation values compared with interpretations presented in the previous studies. For waters in the Prescott and Chino Valley area, more information is needed to understand local controls on stable isotope values related to elevation.

Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

Science.gov (United States)

Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

2013-07-19

Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

What is the effect of variations optimization of the transition state on α-deuterium secondary kinetic isotope effects? A prototype: CD3H + H right-reversible CD3 + H2

International Nuclear Information System (INIS)

Lu, Dahong; Maurice, D.; Truhlar, D.G.

1990-01-01

Variational Transition state theory calculations with semiclassical transmission coefficients have been carried out for a prototype case of α-deuterium secondary kinetic isotope effects (KIEs) in a reaction involving the transformation of an sp 3 carbon to sp 2 , in particular for the reactions of CH 4 and CD 3 H with H and D. The authors also study the KIE for the reverse direction and for the reactions of CH 4 and CD 3 H with D. They find that the variational transition states lead to significantly different nontunneling KIEs than the conventional ones, e.g., 1.22 vs. 1.07, and the inclusion of multidimensional tunneling effects increases the discrepancy even more. The origins of these variations and tunneling effects are examined in detail in terms of structures, vibrational frequencies, and the curvature of the reaction path. The conclusions have wide implications for the validity of conventional treatments of kinetic isotope effects. They predict some particularly large secondary KIEs at low temperature, and these predictions can be tested by future experiments

CO and H2 uptake and emissions by soil: variability of fluxes and their isotopic signatures

Science.gov (United States)

Popa, Maria Elena; Chen, Qianjie; Ferrero Lopez, Noelia; Röckmann, Thomas

2017-04-01

In order to study the uptake and release of H2 and CO by soil, we performed long term, high frequency measurements with an automatic soil chamber at two sites in the Netherlands (Cabauw - grassland, and Speuld - forest). The measurements were performed over different seasons and cover in total a cumulated interval of about one year. These measurements allow determining separately, for each species, the two distinct fluxes i.e. uptake and release, and investigating their temporal variability and dependencies on environmental variables. Additional experiments were performed for determining the isotopic signatures of the H2 and CO uptake and release by soil. Flask samples were filled from the soil chamber, and then analyzed in the laboratory for the stable isotopic composition of H2 (δD) and CO (δ13C and δ18O). We find that both uptake and release are present at all times, regardless of the direction of the net flux. The emissions are significant for both species and at Cabauw, there are times and places where emissions outweigh the soil uptake. For each species, the two fluxes have different behavior and dependence on external variables, which indicates that they have different origins. The isotope results also support that, for both H2 and CO, uptake and emission occur simultaneously. We were able to determine separately the isotopic effects of the two fluxes. For both H2 and CO, soil uptake is associated with a small positive fractionation (the lighter molecule is taken up faster). The soil uptake fractionation (α = kheavy/klight) was 0.945 ± 0.004 for H2; for CO, the fractionation was 0.992 for 13C and 0.985 for 18O. The isotopic composition of the H2 emitted from the grassland was -530 ± 40 ‰, less depleted that what is expected from the isotopic equilibrium of H2 with water. For CO, the isotopic composition of the soil emission is depleted in 13C compared to atmospheric CO, and lower than the average isotopic composition of plant or soil organic matter.

Ab initio calculation of the transition-state properties and addition rate constants for H + C2H2 and selected isotopic analogues

International Nuclear Information System (INIS)

Harding, L.B.; Wagner, A.F.; Bowman, J.M.; Schatz, G.C.; Christoffel, K.

1982-01-01

GVB-POL-CI ab initio calculations of the geometries, energetics, and normal mode frequencies of C 2 H 2 , C 2 H 3 , and the transition state for the addition reaction of H + C 2 H 2 are presented. In addition, normal mode frequencies for the isotopic variants D + C 2 D 2 , D + C 2 H 2 , and H + C 2 D 2 are preented. These results are compared to experimental values for C 2 H 2 and to ab initio values of Hagase and Kern, and semiempirical values of Keil, Lynch, Cowfer, and Michael. The results are also used to calculate the apparent bimolecular addition rate constant using conventional RRKM theory for chemical activation. The calculated rate constants and their isotopic variants are compared as a function of temperature and pressure to available experimental information. The agreement is little different from that obtained by Keil et al. with a similar calculation using semiempirical values for acetylene, transition-state, and vinyl radical properties. In particular, the calculated high-pressure limit of the rate constant appears to be at least 1 order of magnitude higher than the experimental limit. Several possible reasons for this discrepancy are discussed

Kinetic stable Cr isotopic fractionation between aqueous Cr(III)-Cl-H2O complexes at 25 °C: Implications for Cr(III) mobility and isotopic variations in modern and ancient natural systems

Science.gov (United States)

Babechuk, Michael G.; Kleinhanns, Ilka C.; Reitter, Elmar; Schoenberg, Ronny

2018-02-01

dissolution of two Cr(III)-Cl solids (dried NIST SRM979 standard and commercial CrCl3·6H2O salt) in 0.01 M HCl (pH ≈ 2). The ε53/52Cr(CrCl2+/CrCl2+) for the CrCl2+ to CrCl2+ reaction is -0.19‰ (SRM979) and -0.38‰ (salt) and the ε53/52Cr(Cr3+/CrCl2+) for the CrCl2+ to Cr3+ reaction is consistent for both experiments at -0.49‰ (SRM979) and -0.51‰ (salt). Experiments where SRM979 is dissolved in 0.1 and 1 M HCl for a longer aging period provide preliminary evidence that the Cr3+/CrCl2+ Cr(III) isotopic fractionation scales with HCl concentration (transformation rate). Chromium(III) dissolved in 6 M HCl and aged 5 months still yields an inter-species Cr isotope distribution that is apparently inherited from kinetic effects (light Cr isotopes in Cr3+), attesting to the slow development of inter-species isotopic equilibrium, which instead predicts progressively heavier Cr isotopes from CrCl2+ to CrCl2+ to Cr3+. The kinetic Cr(III) isotopic fractionation documented herein is proposed to be relevant to understanding systems where aqueous Cr(III)-Cl species may be temporarily stable (e.g., metamorphic and hydrothermal systems or lateritic weathering). Further, the complexation of Cr(III) with other ligands (e.g., CO32-, organics), combined with additional kinetic effects of Cr(III) potentially occurring in soils or sediment, must be explored prior to establishing the significance of empirical stable Cr isotope signatures in marine and continental environments. Further understanding of non-redox effects may lead to stable Cr isotopes developing as a proxy for system pH or ligand chemistry.

Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

International Nuclear Information System (INIS)

Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

2012-01-01

Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the (NiFe)-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

H/D isotope effects in high temperature proton conductors

DEFF Research Database (Denmark)

Bonanos, Nikolaos; Huijser, A.; Poulsen, Finn Willy

2015-01-01

The atomic mass ratio of ca. 2 between deuterium and hydrogen is the highest for any pair of stable isotopes and results in significant and measurable H/D isotope effects in high temperature proton conductors containing these species. This paper discusses H/D isotope effects manifested in O-H/O-D...

Isotope analysis of diamond-surface passivation effect of high-temperature H2O-grown atomic layer deposition-Al2O3 films

International Nuclear Information System (INIS)

Hiraiwa, Atsushi; Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi

2015-01-01

The Al 2 O 3 film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H 2 O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D 2 O instead of H 2 O in the ALD and found that the Al 2 O 3 film formed at a conventional temperature (100 °C) incorporates 50 times more CH 3 groups than the high-temperature film. This CH 3 is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H 2 O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H 2 O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D 2 O-oxidant ALD but found that the mass density and dielectric constant of D 2 O-grown Al 2 O 3 films are smaller than those of H 2 O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al 2 O 3 films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD

Climatic and geographical dependence of the H, C and O stable isotope ratios of Italian wine

International Nuclear Information System (INIS)

Camin, Federica; Dordevic, Nikola; Wehrens, Ron; Neteler, Markus; Delucchi, Luca; Postma, Geert; Buydens, Lutgarde

2015-01-01

Graphical abstract: Correlation matrix between (D/H) 1 , (D/H) 2 , δ 13 C and δ 18 O parameters of wine (4000 samples) and the climatic and geographical characteristics of the areas of origin. - Highlights: • We studied the relationship between wine isotopic data and climate and geography. • We considered (D/H) 1 , (D/H) 2 and δ 13 C of ethanol and δ 18 O of water of 4000 wines. • δ 18 O, followed by (D/H) 1 , had the strongest relationship with climate and location. • The dominant variables were latitude, δ 18 O and δ 2 H of precipitation and temperature. • Relationships and models may be used to predict the isotopic composition of wine. - Abstract: In this study, we investigated the relationship between (D/H) 1, (D/H) 2 and δ 13 C of ethanol and δ 18 O of water in wine, and variables describing the climate and the geography of the production area, using exploratory visualisation tools, regression analysis and linear modelling. For the first time, a large amount of data (around 4000 wine samples collected over 11 years in Italy) and all the official isotopic parameters, as well as a large number of significant climatic and geographical descriptors (date of harvest, latitude, longitude, elevation, distance from the sea, amount of precipitation, maximum daily temperature, minimum daily temperature, mean daily temperature, δ 18 O and δ 2 H of precipitation) were considered. δ 18 O, followed by (D/H) 1 , was shown to have the strongest relationship with climate and location. The dominant variables were latitude, with a negative relationship, δ 18 O and δ 2 H of precipitation and temperature, both with positive relationships. The identified correlations and models could be used to predict the isotopic composition of authentic wines, offering increased possibilities for detecting fraud and mislabelling

{sup 18}O, {sup 2}H and {sup 3}H isotopic composition of precipitation and shallow groundwater in Olkiluoto

Energy Technology Data Exchange (ETDEWEB)

Hendriksson, N. [Geological Survey of Finland, Espoo (Finland); Karhu, J.; Niinikoski, P. [Univ. of Helsinki (Finland)

2014-12-15

The isotopic composition of oxygen and hydrogen in local precipitation is a key parameter in the modelling of local water circulation. This study was initiated in order to provide systematic monthly records of the isotope content of atmospheric precipitation in the Olkiluoto area and to establish the relation between local rainfall and newly formed groundwater. During January 2005 - December 2012, a total of 85 cumulative monthly rainfall samples and 68 shallow groundwater samples were collected and the isotopic composition of oxygen and hydrogen was recorded for all those samples. Tritium values are available for 79 precipitation and 65 groundwater samples. Based on the 8-year monitoring, the long-term weighted annual mean isotope values of precipitation and the mean values of shallow groundwater are -11.59 per mille and -11.27 per mille for δ{sup 18}O, - 82.3 per mille and -80.3 per mille for δ{sup 2}H and 9.8 and 9.1 TU for tritium, respectively. Based on these data, the mean stable isotope ratios of groundwater represent the long-term mean annual isotopic composition of local precipitation. The precipitation data were used to establish the local meteoric water line (LMWL) for the Olkiluoto area. The line is formulated as: δ{sup 2}H = 7.45 star δ{sup 18}O + 3.82. The isotope time series reveal a change in time. The increasing trend for the δ{sup 18}O and δ{sup 2}H values may be related to climatic variability while the gradual decline observed in the {sup 3}H data is attributed to the still continuing decrease in atmospheric {sup 3}H activity in the northern hemisphere. The systematic seasonal and long-term tritium trends suggest that any potential ground-level tritium release from the Olkiluoto nuclear power plants is insignificant. The d-excess values of Olkiluoto precipitation during the summer period indicated that a notable amount of re-cycled Baltic Sea water may have contributed to precipitation in the Finnish southern coast. Preliminary estimates

Comparison of SAS3A and MELT-III predictions for a transient overpower hypothetical accident

International Nuclear Information System (INIS)

Wilburn, N.P.

1976-01-01

A comparison is made of the predictions of the two major codes SAS3A and MELT-III for the hypothetical unprotected transient overpower accident in the FFTF. The predictions of temperatures, fuel restructuring, fuel melting, reactivity feedbacks, and core power are compared

Application of 18O and 2H natural isotopes for groundwater study in Semarang Basin, Central Java

International Nuclear Information System (INIS)

Rasi Prasetio; Satrio

2015-01-01

As a big city that support industrialism, Semarang has increasing needs of fresh water supply which is mostly provided by ground water. The utilization of groundwater must consider sustainability and environmental preservation aspects, as water is basic needs for human being. Therefore, the knowledge about groundwater dynamics is important to manage groundwater utilization. Isotope hydrology technique using 18 O and 2 H isotopes has been applied to investigate groundwater dynamics and can be taken as consideration for groundwater management. For this purpose, water samples have been collected from various water sources such as springs, deep monitoring wells, dug wells, streams and rain water for 18 O and 2 H isotopes analysis. The results show that isotopes composition of groundwater varied between -8.77‰ to -4.76‰ for δ 18 O and -56.6‰ to -29.4‰ for δ 2 H. Isotopes composition for unconfined groundwater in most of study area are relatively uniform, i.e. between -5.9‰ to -6.6‰ for δ 18 O and -35.1‰ to -40.4‰ for δ 2 H, except in some minor places that have more depleted and more enriched composition. This distribution indicates that the unconfined aquifer is depend on local recharge. While most of isotopes composition of deep confined aquifer plotted around isotopes composition of Ungaran's rain water, indicates that the recharge area of these confined groundwater were originated from this elevation or higher. (author)

Nyheder i SAS Analytics 14.2

DEFF Research Database (Denmark)

Milhøj, Anders

2017-01-01

I november 2016 blev Analytical Produts i den opdaterede version 14.2 sendt på markedet. Denne opdatering indeholder opdateringer af de analytiske programpakker inden for statistik, økonometri, operationsanalyse etc. Disse opdateringer er nu løsrevet fra samtidige opdateringer af det samlede SAS-program...

Climatic and geographical dependence of the H, C and O stable isotope ratios of Italian wine

Energy Technology Data Exchange (ETDEWEB)

Camin, Federica, E-mail: federica.camin@fmach.it [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Dordevic, Nikola [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Radboud University Nijmegen, Institute for Molecules and Materials, Analytical Chemistry, P.O. Box 9010, 6500 GL Nijmegen (Netherlands); Wehrens, Ron; Neteler, Markus; Delucchi, Luca [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Postma, Geert; Buydens, Lutgarde [Radboud University Nijmegen, Institute for Molecules and Materials, Analytical Chemistry, P.O. Box 9010, 6500 GL Nijmegen (Netherlands)

2015-01-01

Graphical abstract: Correlation matrix between (D/H){sub 1}, (D/H){sub 2}, δ{sup 13}C and δ{sup 18}O parameters of wine (4000 samples) and the climatic and geographical characteristics of the areas of origin. - Highlights: • We studied the relationship between wine isotopic data and climate and geography. • We considered (D/H){sub 1}, (D/H){sub 2} and δ{sup 13}C of ethanol and δ{sup 18}O of water of 4000 wines. • δ{sup 18}O, followed by (D/H){sub 1}, had the strongest relationship with climate and location. • The dominant variables were latitude, δ{sup 18}O and δ{sup 2}H of precipitation and temperature. • Relationships and models may be used to predict the isotopic composition of wine. - Abstract: In this study, we investigated the relationship between (D/H){sub 1,} (D/H){sub 2} and δ{sup 13}C of ethanol and δ{sup 18}O of water in wine, and variables describing the climate and the geography of the production area, using exploratory visualisation tools, regression analysis and linear modelling. For the first time, a large amount of data (around 4000 wine samples collected over 11 years in Italy) and all the official isotopic parameters, as well as a large number of significant climatic and geographical descriptors (date of harvest, latitude, longitude, elevation, distance from the sea, amount of precipitation, maximum daily temperature, minimum daily temperature, mean daily temperature, δ{sup 18}O and δ{sup 2}H of precipitation) were considered. δ{sup 18}O, followed by (D/H){sub 1}, was shown to have the strongest relationship with climate and location. The dominant variables were latitude, with a negative relationship, δ{sup 18}O and δ{sup 2}H of precipitation and temperature, both with positive relationships. The identified correlations and models could be used to predict the isotopic composition of authentic wines, offering increased possibilities for detecting fraud and mislabelling.

Isotopic and criticality validation for actinide-only burnup credit

International Nuclear Information System (INIS)

Fuentes, E.; Lancaster, D.; Rahimi, M.

1997-01-01

The techniques used for actinide-only burnup credit isotopic validation and criticality validation are presented and discussed. Trending analyses have been incorporated into both methodologies, requiring biases and uncertainties to be treated as a function of the trending parameters. The isotopic validation is demonstrated using the SAS2H module of SCALE 4.2, with the 27BURNUPLIB cross section library; correction factors are presented for each of the actinides in the burnup credit methodology. For the criticality validation, the demonstration is performed with the CSAS module of SCALE 4.2 and the 27BURNUPLIB, resulting in a validated upper safety limit

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

Science.gov (United States)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

H/D Isotope Effects in Hydrogen Bonded Systems

Directory of Open Access Journals (Sweden)

Aleksander Filarowski

2013-04-01

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

CRC DEPLETION CALCULATIONS FOR THE NON-RODDED ASSEMBLIES IN BATCHES 1, 2, AND 3 OF CRYSTAL RIVER UNIT 3

International Nuclear Information System (INIS)

Wright, Kenneth D.

1997-01-01

The purpose of this design analysis is to document the SAS2H depletion calculations of certain non-rodded fuel assemblies from batches 1, 2, and 3 of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for Commercial Reactor Critical (CRC) evaluations to support development of the disposal criticality methodology. A non-rodded assembly is one which never contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) during its irradiation history. The objective of this analysis is to provide SAS2H generated isotopic compositions for each fuel assembly's depleted fuel and depleted burnable poison materials. These SAS2H generated isotopic compositions are acceptable for use in CRC benchmark reactivity calculations containing the various fuel assemblies

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the "2H abundance

International Nuclear Information System (INIS)

Faghihi, V.; Aerts-Bijma, A.T.; Jansen, H.G.; Spriensma, J.J.; Meijer, H.A.J.; Peruzzi, A.; Geel, J. van

2015-01-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the "2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of "2H isotopic abundances encompassing widely the natural abundance range, while the "1"8O and "1"7O isotopic abundance were kept approximately constant and the "1"8O - "1"7O ratio was close to the Meijer-Li relationship for natural waters. The selected range of "2H isotopic abundances led to cells that realised TPW temperatures between approximately -140 μK to + 2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ"2H correction parameter of A_2_H = 673 μK/(per thousand deviation of δ"2H from VSMOW) with a combined uncertainty of 4 μK (k = 1, or 1 s). (authors)

Anomalous H/D isotope effect on 35Cl NQR frequencies and H/D isotope effect on 1H MAS NMR spectra in pyrrolidinium p-chlorobenzoate

International Nuclear Information System (INIS)

Nakano, Ryo; Honda, Hisashi; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Kimura, Taiki; Kyo, Shin-shin; Ishimaru, Shin'ichi; Miyake, Ryosuke

2010-01-01

An anomalous isotope effect was observed in the 35 Cl NQR frequency of pyrrolidinium p-chlorobenzoate (C 4 H 8 NH 2 + ·ClC 6 H 4 COO - ) by deuterium substitution of hydrogen atoms which form two kinds of N-H...O type hydrogen bonds. Large negative frequency shifts of the 35 Cl resonance lines, reaching 309 kHz at 77 K and 267 kHz at 293 K, were obtained upon deuteration, although the Cl atom in the molecule formed no hydrogen bonds in the crystal. 1 H MAS NMR lines showed significant changes by the deuterium substitution, while in contrast, small shifts of 13 C CP/MAS NMR signals were obtained. Our measurements of 1 H NMR spin-lattice relaxation times (T 1 ) suggested that the H/D isotope shifts detected from the 35 Cl NQR frequencies and 1 H NMR spectra are due to structural changes rather than molecular dynamics. Single-crystal X-ray diffraction measurements showed two remarkable H/D isotope differences in the molecular arrangements, (1) the N-H length along the crystallographic a axis became 1 pm shorter, and (2) the dihedral angle between benzene and the pyrrolidine ring changed by 1.1(2)deg upon deuteration. Using density functional theory estimations, the anomalous 35 Cl NQR frequency shifts and 1 H MAS NMR line-shape changes could be explained by the dihedral angle change rather than the N-H length difference. (author)

Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

International Nuclear Information System (INIS)

Gerster, Richard

1971-01-01

The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

Implementation, verification, and validation of the FPIN2 metal fuel pin mechanics model in the SASSYS/SAS4A LMR transient analysis codes

International Nuclear Information System (INIS)

Sofu, T.; Kramer, J.M.

1994-01-01

The metal fuel version of the FPIN2 code which provides a validated pin mechanics model is coupled with SASSYS/SAS4A Version 3.0 for single pin calculations. In this implementation, SASSY/SAS4A provides pin temperatures, and FPIN2 performs analysis of pin deformation and predicts the time and location of cladding failure. FPIN2 results are also used for the estimates of axial expansion of fuel and associated reactivity effects. The revalidation of the integrated SAS-FPIN2 code system is performed using TREAT tests

INVESTIGATION OF STABLE ISOTOPE OF 18O AND 2H IN SHALLOW GROUNDWATER FROM KARAWANG AREA

Directory of Open Access Journals (Sweden)

E. Ristin Pujiindiyati

2010-06-01

Full Text Available Karawang area is well known as an agriculture area and 2% area is utilized for industries. Clean water demands increase due to developing industry development and population increasement. The origin of groundwater is necessary to keep the sustainability of water resources in this area. Stable isotopes such as 18O and 2H can be used as a parameter to trace the ground water origin. The methods used were Epstein-Mayeda and Zinc reduction for analysis 18O and 2H, respectively. Sampling period was conducted in major dry season in year 2002. The result showed that evaporation effect had influenced to the content of both isotopes in its shallow groundwater that caused a slope shift from its local meteoric line. The origin of its shallow groundwater was from rainwater infiltrating directly in less than 10 m altitude. Citarum River showed more depleted values in both isotopes compared to shallow groundwater and it indicated that its water might originate from spring at the altitude of 600 m.     Keywords: oxygene-18, deuterium, groundwater, isotope

Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

Energy Technology Data Exchange (ETDEWEB)

Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp [Institute for Nanoscience and Nanotechnology, Waseda University, 513 Waseda-tsurumaki, Shinjuku, Tokyo 162-0041 (Japan); Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi, E-mail: kawarada@waseda.jp [Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555 (Japan)

2015-06-07

The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups than the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of

SAS for dummies

CERN Document Server

McDaniel, Stephen

2010-01-01

The fun and easy way to learn to use this leading business intelligence tool Written by an author team who is directly involved with SAS, this easy-to-follow guide is fully updated for the latest release of SAS and covers just what you need to put this popular software to work in your business. SAS allows any business or enterprise to improve data delivery, analysis, reporting, movement across a company, data mining, forecasting, statistical analysis, and more. SAS For Dummies, 2nd Edition  gives you the necessary background on what SAS can do for you and explains how to use the Enterprise Guide. SAS provides statistical and data analysis tools to help you deal with all kinds of data: operational, financial, performance, and more Places special emphasis on Enterprise Guide and other analytical tools, covering all commonly used features Covers all commonly used features and shows you the practical applications you can put to work in your business Explores how to get various types of data into the software and...

SAS4A and FPIN2X validation for slow ramp TOP accidents: experiments TS-1 and TS-2

International Nuclear Information System (INIS)

Hill, D.J.

1986-01-01

The purpose of this paper is to present further results in the series of experimental analyses being performed using SAS4A and FPIN2X in order to provide a systematic validation of these codes. The two experiments discussed here, TS-1 and TS-2, were performed by Westinghouse Hanford/Hanford Engineering Development Laboratory (WHC/HEDL) in the Transient Reactor Test (TREAT) Facility. They were slow ramp transient overpowers (TOPs) of ∼ 5 cent/s equivalent Fast Flux Test Facility (FFTF) ramp rate, single-pin experiments in flowing sodium loops. The good agreement found here adds significantly to the experimental data base that provides the foundation for SAS4A and FPIN2X validation. It also shows that prefailure internal fuel motion is a phenomenon that has to be correctly accounted for, not only as a potential inherent safety mechanism, but also before any accurate prediction of fuel failure and subsequent fuel motion and the associated reactivity effects can be made. This is also true for metal-fueled pins. This capability is provided by PINACLE, which is being incorporated into SAS4A

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

Science.gov (United States)

Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

2015-12-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

On the basic substances used in the separation process by isotope exchange H2S - H2O, at two temperatures, in view of producing heavy water

International Nuclear Information System (INIS)

Popescu, V.

1977-01-01

In view of producing heavy water, the influence of the deuterium proportion in the basic substances, on the efficiency of the isotope exchange process H 2 S - H 2 O for two temperatures was studied. Heavy water is extracted from ordinary water and concentrated from 0.014 per cent to 5-15 per cent D 2 O by isotope bithermal exchange with the hydrogen sulphite. Theoretical and experimental research was carried out in laboratories and then applied on a pilot plant by designing and testing a drying equipment for hydrogen sulphite. The maximum H 2 S concentration rose to 99.84 per cent. The purity of the hydrogen sulphite resulting from the pilot plant, as well as the optimization of the installation for producing H 2 S depending on the deuterium distribution, make sure that the two methods for the preparation of sodium sulphite and hydrogen sulphite can be applied in industry. (author)

2ΔH(D) and 1ΔN(D) isotope effects on nuclear shielding of ammonium ions in complexes with crown ethers and cryptands

International Nuclear Information System (INIS)

Hansen, P.E.; Hansen, Aa.E.; Lycka, A.; Buvari-Barcza, A.

1993-01-01

One-bond deuterium isotope effects on nitrogen nuclear shielding, 1 ΔN(D) and two-bond isotope effects at 1 H nuclear shielding, 2 ΔH(D), have been investigated in a series of inclusion complexes. The hosts comprise, SC-24, [2.2.2], [2.2.1], [2.2.1] D, [2.2] DD, K5, 18-crown-6 and 18-crown-6 tetracarboxylic acid. The structure of the host [2.2.1] is discussed based on isotope effects and 1 H chemical shifts, and an interesting exchange reaction is observed between CDCl 3 and ammonium ions in the [2.2.1] complex. The counterion dependence is shown to be zero for ammonium ions fully included in cages such as SC-24 and [2.2.2] and for 18-C-6(COOH) 4 . For cryptands and podands such as [2.2.1] and K5 a weak counterion dependence of 2 ΔH(D) opposite to that found for ammonium ions in water is observed, while 1 ΔN(D) and 15 N chemical shifts depend very strongly on the counterions, as also found for ammonium ions in water solution. The anilinium ion shows effects similar to those observed for the ammonium ion. 1 ΔN(D) isotope effects correlate well with δN and 2 ΔH(D) correlate with δNH. The correlation between 1 ΔN(D) and 2 ΔH(D) is different for ammonium ions in water and ions included in crowns, cryptands or podands. This shows that different mechanisms are operating. The 2 ΔH(D) isotope effects and δNH chemical shifts depend on the distance to the nearest acceptor (oxygen or nitrogen), and they also depend on the type of acceptor. 2 ΔH(D) isotope effects are found to be a good gauge of N ... N or N ... O distances of the inclusion complexes. The 2 ΔH(D) isotope effects vary with temperature, but the dramatic changes in the 1 H NMR spectra of the host are not reflected in the isotope effects. The one-bond couplings, 1 J(N,H), correlate with 2 ΔH(D). The variations are much larger for the cryptands than found in water solutions. (au) (50 refs.)

Electrochemical H-D isotope effect at metal-perovskite proton conductor interfaces

DEFF Research Database (Denmark)

Kek, D.; Bonanos, N.

1999-01-01

The H-D isotope effect on the electrode kinetics of a metal-proton conductor interface has been investigated. The current-voltage behaviour depends on the nature of the electrode (Ni, Ag), the atmosphere (H(2), D(2)), the partial pressures of the gases, and the temperature. The isotope effect was...

Affordable uniform isotope labeling with 2H, 13C and 15N in insect cells

International Nuclear Information System (INIS)

Sitarska, Agnieszka; Skora, Lukasz; Klopp, Julia; Roest, Susan; Fernández, César; Shrestha, Binesh; Gossert, Alvar D.

2015-01-01

For a wide range of proteins of high interest, the major obstacle for NMR studies is the lack of an affordable eukaryotic expression system for isotope labeling. Here, a simple and affordable protocol is presented to produce uniform labeled proteins in the most prevalent eukaryotic expression system for structural biology, namely Spodoptera frugiperda insect cells. Incorporation levels of 80 % can be achieved for 15 N and 13 C with yields comparable to expression in full media. For 2 H, 15 N and 2 H, 13 C, 15 N labeling, incorporation is only slightly lower with 75 and 73 %, respectively, and yields are typically twofold reduced. The media were optimized for isotope incorporation, reproducibility, simplicity and cost. High isotope incorporation levels for all labeling patterns are achieved by using labeled algal amino acid extracts and exploiting well-known biochemical pathways. The final formulation consists of just five commercially available components, at costs 12-fold lower than labeling media from vendors. The approach was applied to several cytosolic and secreted target proteins

Variation of δ2H, δ18O & δ13C in crude palm oil from different regions in Malaysia: Potential of stable isotope signatures as a key traceability parameter.

Science.gov (United States)

Muhammad, Syahidah Akmal; Seow, Eng-Keng; Mohd Omar, A K; Rodhi, Ainolsyakira Mohd; Mat Hassan, Hasnuri; Lalung, Japareng; Lee, Sze-Chi; Ibrahim, Baharudin

2018-01-01

A total of 33 crude palm oil samples were randomly collected from different regions in Malaysia. Stable carbon isotopic composition (δ 13 C) was determined using Flash 2000 elemental analyzer while hydrogen and oxygen isotopic compositions (δ 2 H and δ 18 O) were analyzed by Thermo Finnigan TC/EA, wherein both instruments were coupled to an isotope ratio mass spectrometer. The bulk δ 2 H, δ 18 O and δ 13 C of the samples were analyzed by Hierarchical Cluster Analysis (HCA), Principal Component Analysis (PCA) and Orthogonal Partial Least Square-Discriminant Analysis (OPLS-DA). Unsupervised HCA and PCA methods have demonstrated that crude palm oil samples were grouped into clusters according to respective state. A predictive model was constructed by supervised OPLS-DA with good predictive power of 52.60%. Robustness of the predictive model was validated with overall accuracy of 71.43%. Blind test samples were correctly assigned to their respective cluster except for samples from southern region. δ 18 O was proposed as the promising discriminatory marker for discerning crude palm oil samples obtained from different regions. Stable isotopes profile was proven to be useful for origin traceability of crude palm oil samples at a narrower geographical area, i.e. based on regions in Malaysia. Predictive power and accuracy of the predictive model was expected to improve with the increase in sample size. Conclusively, the results in this study has fulfilled the main objective of this work where the simple approach of combining stable isotope analysis with chemometrics can be used to discriminate crude palm oil samples obtained from different regions in Malaysia. Overall, this study shows the feasibility of this approach to be used as a traceability assessment of crude palm oils. Copyright © 2017 The Chartered Society of Forensic Sciences. Published by Elsevier B.V. All rights reserved.

USGS48 Puerto Rico precipitation - A new isotopic reference material for δ2H and δ18O measurements of water

Science.gov (United States)

Qi, Haiping; Coplen, Tyler B.; Tarbox, Lauren V.; Lorenz, Jennifer M.; Scholl, Martha A.

2014-01-01

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ2H and δ18O values of this reference water are−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ2H and δ18O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty (U=2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

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

Directory of Open Access Journals (Sweden)

Brian J. Campbell

2017-10-01

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

Isotopic identification and quantification of seawater influx into a groundwater body using environmental isotopes (2H,18O)

International Nuclear Information System (INIS)

Stichler, W.; Weise, S.M.; Trimborn, P.

2001-01-01

The development of optimal strategies for groundwater protection and for minimising the danger to groundwater through raw material excavation presupposes a well-founded hydrogeological knowledge of the complex interactions between flooded gravel pit and groundwater. The present study was dedicated to a quantitative determination of the groundwater throughput of a representative flooded gravel pit, the Alte Vogelbaggersee, on the basis of isotope experiments. Water samples were taken from groundwater analysis points upstream and downstream of the gravel pit and in the pit itself over a two-year observation period. In addition to isotope analysis ( 2 H, 1 8O) the scope of measurements included local parameters and chemical analysis in vertical profiles, time series and spatial distributions on selected days [de

Syntheses of [5-2H]-uracil, [5-2H]-cytosine, [6-2H]-uracil and [6-2H]-cytosine

International Nuclear Information System (INIS)

Kiritani, Reiko; Asano, Takeyoshi; Fujita, Shin-ichi; Dohmaru, Takaaki; Kawanishi, Tetsuro

1986-01-01

Syntheses of [5- 2 H]-, [6- 2 H]-uracil and [5- 2 H]-, [6- 2 H]-cytosine were investigated. The catalytic reaction of uracil or cytosine with 2 H 2 gas in alkaline media gave rise to [6- 2 H]-compounds almost exclusively. On the other hand, the reaction of 5-bromouracil or 5-bromocytosine with 2 H 2 gas gave rise to a mixture of [5- 2 H]-, [6- 2 H]- and [5- 2 H, 6- 2 H]-compounds depending on the experimental conditions. By controlling the temperature, the pressure of 2 H 2 gas and the amount of catalyst, [5- 2 H]-uracil and [5- 2 H]-cytosine were obtained. The isotopic distribution in each product was measured by 1 H NMR spectroscopy combined with an HPLC method. (author)

Solvent 1H/2H isotopic effects in the reaction of the L-Tyrosine oxidation catalyzed by Tyrosinase

International Nuclear Information System (INIS)

Kozlowska, M.; Kanska, M.

2006-01-01

Tyrosinase is well known catalyst in the oxidation of L-Tyrosine to L-DOPA and following oxidation of L-DOPA to dopachinone. The aim of communication is to present the results of studies on the solvent isotopic effects (SIE) in the above reactions for the 1 H/ 2 H in the 3',5' and 2',6' substituted tyrosine. Obtained dependence of the reaction rate on the substrate concentration were applied for optimization of the kinetic parameters, k cat and k cat /K m , in the Michaelis-Menten equation. As a result - better understanding of the L-DOPA creation can be achieved

A combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic air

Directory of Open Access Journals (Sweden)

H. Schaefer

2012-09-01

Full Text Available Isotope records of atmospheric CH4 can be used to infer changes in the biogeochemistry of CH4. One factor currently limiting the quantitative interpretation of such changes are uncertainties in the isotope measurements stemming from the lack of a unique isotope reference gas, certified for δ13C-CH4 or δ2H-CH4. We present a method to produce isotope reference gases for CH4 in synthetic air that are precisely anchored to the VPDB and VSMOW scales and have δ13C-CH4 values typical for the modern and glacial atmosphere. We quantitatively combusted two pure CH4 gases from fossil and biogenic sources and determined the δ13C and δ2H values of the produced CO2 and H2O relative to the VPDB and VSMOW scales within a very small analytical uncertainty of 0.04‰ and 0.7‰, respectively. We found isotope ratios of −39.56‰ and −56.37‰ for δ13C and −170.1‰ and −317.4‰ for δ2H in the fossil and biogenic CH4, respectively. We used both CH4 types as parental gases from which we mixed two filial CH4 gases. Their δ13C was determined to be −42.21‰ and −47.25‰ representing glacial and present atmospheric δ13C-CH4. The δ2H isotope ratios of the filial CH4 gases were found to be −193.1‰ and −237.1‰, respectively. Next, we mixed aliquots of the filial CH4 gases with ultrapure N2/O2 (CH4 ≤ 2 ppb producing two isotope reference gases of synthetic air with CH4 mixing ratios near atmospheric values. We show that our method is reproducible and does not introduce isotopic fractionation for δ13C within the uncertainties of our detection limit (we cannot conclude this for δ2H because our system is currently not prepared for δ2H-CH4 measurements in air samples. The general principle of our method can be applied to produce synthetic isotope reference gases targeting δ2H-CH4 or other gas species.

SAS essentials mastering SAS for data analytics

CERN Document Server

Elliott, Alan C

2015-01-01

A step-by-step introduction to using SAS® statistical software as a foundational approach to data analysis and interpretation Presenting a straightforward introduction from the ground up, SAS® Essentials: Mastering SAS for Data Analytics, Second Edition illustrates SAS using hands-on learning techniques and numerous real-world examples. Keeping different experience levels in mind, the highly-qualified author team has developed the book over 20 years of teaching introductory SAS courses. Divided into two sections, the first part of the book provides an introduction to data manipulation, st

Molecular hydrogen (H2) combustion emissions and their isotope (D/H) signatures from domestic heaters, diesel vehicle engines, waste incinerator plants, and biomass burning

NARCIS (Netherlands)

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

2012-01-01

Molecular hydrogen (H2), its stable isotope signature ( D), and the key combustion parameters carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were measured from various combustion processes. H2 in the exhaust of gas and oil-fired heaters and of waste incinerator plants was generally

The ground state infrared spectra of several isotopic forms of the CdH and ZnH radicals

International Nuclear Information System (INIS)

Urban, R.; Magg, U.; Birk, H.; Jones, H.

1990-01-01

The infrared spectra of six isotopic forms of cadmium monohydride, [ 116 CdH (7.6%), 114 CdH (28.9%), 113 CdH (12.3%), 112 CdH (24.1%), 111 CdH (12.7%), and 110 CdH (12.4%)] and four isotopic forms of zinc hydride [ 68 ZnH (18.6%), 67 ZnH (4.1%), 66 ZnH (27.8%), and 64 ZnH (48.9%)] have been observed in natural abundance in their ground electronic state ( 2 Σ + ) in the gas phase using a diode laser spectrometer. A number of transitions of 108 CdH (0.9%) and 106 CdH (1.2%) and 70 ZnH (0.6%) were also observed, but too little data was accumulated to allow a good analysis. The hydrides were produced by reaction of hydrogen with metal vapor at elevated temperature in an electric discharge. The analysis of the experimental data was carried out in two ways. (a) A complete set of Dunham parameters and spin--rotation parameters (γ parameters) was determined for each isotopic species of the two radicals and (b) a set of mass-independent parameters were calculated for both ZnH and CdH. Since only information over the isotopic species of the heavy atom was produced in each case, effects arising from a breakdown of the Born--Oppenheimer approximation were negligible. The effects of the strong anharmonicity present in these two molecules on the values of the parameters are discussed

Laboratory isotopic behaviour (2H, 18O) of sediments pore water during evaporation

International Nuclear Information System (INIS)

Ciolzyk, A.; Bariac, T.; Klamecki, A.; Jusserand, C.

1987-01-01

Two bare sediments (sand and loam) wetted with water of known isotopic composition have been subjected to evaporation in laboratory conditions. An attempt of application of classical isotopic evaporation models for free waters with reducing reservoir has been made, the better fit implies: a)laminar conditions of the atmosphere in the sediment under evaporation; b) a similar isotopic composition of water vapor as the isotopic composition of the water vapor of the external atmosphere. Variation of ε K and δ V H implies a better knowledge of the complex mechanisms of the atmosphere behaviour in the pore path of porous media under evaporation [fr

Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

Science.gov (United States)

Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

2016-06-30

We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

Prediction of absolute infrared intensities for the fundamental vibrations of H2O2

Science.gov (United States)

Rogers, J. D.; Hillman, J. J.

1981-01-01

Absolute infrared intensities are predicted for the vibrational bands of gas-phase H2O2 by the use of a hydrogen atomic polar tensor transferred from the hydroxyl hydrogen atom of CH3OH. These predicted intensities are compared with intensities predicted by the use of a hydrogen atomic polar tensor transferred from H2O. The predicted relative intensities agree well with published spectra of gas-phase H2O2, and the predicted absolute intensities are expected to be accurate to within at least a factor of two. Among the vibrational degrees of freedom, the antisymmetric O-H bending mode nu(6) is found to be the strongest with a calculated intensity of 60.5 km/mole. The torsional band, a consequence of hindered rotation, is found to be the most intense fundamental with a predicted intensity of 120 km/mole. These results are compared with the recent absolute intensity determinations for the nu(6) band.

The synthesis of [2-3H2] taurine and [2-3H2] hypotaurine

International Nuclear Information System (INIS)

Fellman, J.H.

1981-01-01

The synthesis of [2- 3 H 2 ]-2-aminoethanesulfonate [2- 3 H]-taurine by the reduction of cyanomethanesulfonic acid with tritium gas is described. The conversion of [2- 3 H]-taurine and its 14 C and 35 S isotopic forms to 2-aminoethanesulfinate (hypotaurine) was accomplished by converting taurine to its corresponding sulfonyl chloride and reducing the latter with metallic zinc. (author)

The O and H stable isotope composition of freshwaters in the British Isles. 2. Surface waters and groundwater

Directory of Open Access Journals (Sweden)

W. G. Darling

2003-01-01

Full Text Available The utility of stable isotopes as tracers of the water molecule has a long pedigree. The study reported here is part of an attempt to establish a comprehensive isotopic 'baseline' for the British Isles as background data for a range of applications. Part 1 of this study (Darling and Talbot, 2003 considered the isotopic composition of rainfall in Britain and Ireland. The present paper is concerned with the composition of surface waters and groundwater. In isotopic terms, surface waters (other than some upland streams are poorly characterised in the British Isles; their potential variability has yet to be widely used as an aid in hydrological research. In what may be the first study of a major British river, a monthly isotopic record of the upper River Thames during 1998 was obtained. This shows high damping of the isotopic variation compared to that in rainfall over most of the year, though significant fluctuations were seen for the autumn months. Smaller rivers such as the Stour and Darent show a more subdued response to the balance between runoff and baseflow. The relationship between the isotopic composition of rainfall and groundwater is also considered. From a limited database, it appears that whereas Chalk groundwater is a representative mixture of weighted average annual rainfall, for Triassic sandstone groundwater there is a seasonal selection of rainfall biased towards isotopically-depleted winter recharge. This may be primarily the result of physical differences between the infiltration characteristics of rock types, though other factors (vegetation, glacial history could be involved. In the main, however, groundwaters appear to be representative of bulk rainfall within an error band of 0.5‰ δ18O. Contour maps of the δ18O and δ2H content of recent groundwaters in the British Isles show a fundamental SW-NE depletion effect modified by topography. The range of measured values, while much smaller than those for rainfall, still covers

Multicomponent DFT study of geometrical H/D isotope effect on hydrogen-bonded organic conductor, κ-H3(Cat EDT-ST)2

Science.gov (United States)

Yamamoto, Kaichi; Kanematsu, Yusuke; Nagashima, Umpei; Ueda, Akira; Mori, Hatsumi; Tachikawa, Masanori

2017-04-01

We theoretically investigated a significant contraction of the hydrogen-bonding O⋯O distance upon H/D substitution in our recently developed purely organic crystals, κ-H3(Cat-EDT-ST)2 (H-ST) and its isotopologue κ-D3(Cat-EDT-ST)2 (D-ST), having π-electron systems coupled with hydrogen-bonding fluctuation. The origin of this geometrical H/D isotope effect was elucidated by using the multicomponent DFT method, which takes the H/D nuclear quantum effect into account. The optimized O⋯O distance in H-ST was found to be longer than that in D-ST due to the anharmonicity of the potential energy curve along the Osbnd H bond direction, which was in reasonable agreement with the experimental trend.

Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

International Nuclear Information System (INIS)

Palin, J.M.; Epstein, S.; Stolper, E.M.

1996-01-01

Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

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

Science.gov (United States)

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

2008-09-21

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

Construction of CARS Spectroscopy for Determination of Isotope shift of Hydrogen H2, D2

International Nuclear Information System (INIS)

Zidan, M. D.; Jazmati, A.; Manni, A.

2007-01-01

Coherent anti-Stokes Raman scattering (CARS) spectrometer has been built. It consists of Raman cell, which is filled with a H2 gas at 5 atm pressure, and a frequency-doubled Nd:YAG laser-pumped dye laser. The two beams are focused by means of a bi-convex 400 mm lens into the Raman cell. The anti-Stokes signal (CARS beam) is generated due to four-wave mixing process. The anti-Stokes signal is directed to a monochrometer entrance slit by prism to be detected by a photomultiplier, which is connected to a computer. The dye laser frequency has to be tuned to satisfy the energy difference between the V 1 beam (Nd:YAG laser beam) and the V 2 beam (the Stokes beam or the dye laser beam) that exactly corresponds to a vibrational or a rotational Raman resonance (E 2 -E 1 ) in the hydrogen molecule, then the anti-Stokes signal ( V 3 ) is generated. The spectra of the anti-Stokes signal has been recorded to determine the isotope shift between H 2 , and D 2 , which is 1161 cm -1 .

Centriolar SAS-7 acts upstream of SPD-2 to regulate centriole assembly and pericentriolar material formation

Science.gov (United States)

Sugioka, Kenji; Hamill, Danielle R; Lowry, Joshua B; McNeely, Marie E; Enrick, Molly; Richter, Alyssa C; Kiebler, Lauren E; Priess, James R; Bowerman, Bruce

2017-01-01

The centriole/basal body is a eukaryotic organelle that plays essential roles in cell division and signaling. Among five known core centriole proteins, SPD-2/Cep192 is the first recruited to the site of daughter centriole formation and regulates the centriolar localization of the other components in C. elegans and in humans. However, the molecular basis for SPD-2 centriolar localization remains unknown. Here, we describe a new centriole component, the coiled-coil protein SAS-7, as a regulator of centriole duplication, assembly and elongation. Intriguingly, our genetic data suggest that SAS-7 is required for daughter centrioles to become competent for duplication, and for mother centrioles to maintain this competence. We also show that SAS-7 binds SPD-2 and regulates SPD-2 centriolar recruitment, while SAS-7 centriolar localization is SPD-2-independent. Furthermore, pericentriolar material (PCM) formation is abnormal in sas-7 mutants, and the PCM-dependent induction of cell polarity that defines the anterior-posterior body axis frequently fails. We conclude that SAS-7 functions at the earliest step in centriole duplication yet identified and plays important roles in the orchestration of centriole and PCM assembly. DOI: http://dx.doi.org/10.7554/eLife.20353.001 PMID:28092264

SAS-1 Is a C2 Domain Protein Critical for Centriole Integrity in C. elegans

Science.gov (United States)

Delattre, Marie; Balestra, Fernando R.; Blanchoud, Simon; Finger, Susanne; Knott, Graham; Müller-Reichert, Thomas; Gönczy, Pierre

2014-01-01

Centrioles are microtubule-based organelles important for the formation of cilia, flagella and centrosomes. Despite progress in understanding the underlying assembly mechanisms, how centriole integrity is ensured is incompletely understood, including in sperm cells, where such integrity is particularly critical. We identified C. elegans sas-1 in a genetic screen as a locus required for bipolar spindle assembly in the early embryo. Our analysis reveals that sperm-derived sas-1 mutant centrioles lose their integrity shortly after fertilization, and that a related defect occurs when maternal sas-1 function is lacking. We establish that sas-1 encodes a C2 domain containing protein that localizes to centrioles in C. elegans, and which can bind and stabilize microtubules when expressed in human cells. Moreover, we uncover that SAS-1 is related to C2CD3, a protein required for complete centriole formation in human cells and affected in a type of oral-facial-digital (OFD) syndrome. PMID:25412110

SAS-1 is a C2 domain protein critical for centriole integrity in C. elegans.

Directory of Open Access Journals (Sweden)

Lukas von Tobel

2014-11-01

Full Text Available Centrioles are microtubule-based organelles important for the formation of cilia, flagella and centrosomes. Despite progress in understanding the underlying assembly mechanisms, how centriole integrity is ensured is incompletely understood, including in sperm cells, where such integrity is particularly critical. We identified C. elegans sas-1 in a genetic screen as a locus required for bipolar spindle assembly in the early embryo. Our analysis reveals that sperm-derived sas-1 mutant centrioles lose their integrity shortly after fertilization, and that a related defect occurs when maternal sas-1 function is lacking. We establish that sas-1 encodes a C2 domain containing protein that localizes to centrioles in C. elegans, and which can bind and stabilize microtubules when expressed in human cells. Moreover, we uncover that SAS-1 is related to C2CD3, a protein required for complete centriole formation in human cells and affected in a type of oral-facial-digital (OFD syndrome.

Combination of functional MRI with SAS and MRA

Energy Technology Data Exchange (ETDEWEB)

Sumida, Masayuki; Takeshita, Shinichirou; Kutsuna, Munenori; Akimitsu, Tomohide; Arita, Kazunori; Kurisu, Kaoru [Hiroshima Univ. (Japan). School of Medicine

1999-02-01

For presurgical diagnosis of brain surface, combination of functional MRI (fMRI) with the MR angiography was examined. This method could visualize brain bay, convolution and vein as index of surface. Five normal adults (male, mean age: 28-year-old) and 7 patients with brain tumor on the main locus to surface (male: 4, female: 3, mean age: 52.3-year-old) were studied. fMRI was performed by SPGR method (TR 70, TE 40, flip angle 60, one slice, thickness 10 mm, FOV 20 cm, matrix 128 x 128). The brain surface was visualized by SAS (surface anatomy scanning). SAS was performed by FSE method (TR 6000, TE 200, echo train 16, thickness 20 mm, slice 3, NEX 2). Cortical veins near superior sagittal sinus were visualized by MRA with 2D-TOF method (TR 50, TE 20, flip angle 60, thickness 2 mm, slice 28, NEX 1). These images were superimposed and functional image of peripheral sensorimotor region was evaluated anatomically. In normal adults, high signal was visualized at another side of near sensorimotor region at 8 of 10 sides. All high signal area of fMRI agreed with cortical vein near sensorimotor region that was visualized by MRA. In patients with brain tumor, signal was visualized at another side of sensorimotor region of tumor without 2 cases with palsy. In another side of tumor, signal of fMRI was visualized in 5 of 7 cases. The tumor was visualized as opposite low signal field in SAS. Locational relation between tumor and brain surface and brain function was visualized distinctly by combination of MRA, SAS and MRA. This method could become useful for presurgical diagnosis. (K.H.)

Water as a solute in aprotic dipolar solvents. 2. D2O-H2O solute isotope effects on the enthalpy of water dissolution in nitromethane, acetonitrile and propylene carbonate at 298.15 K

International Nuclear Information System (INIS)

Ivanov, Evgeniy V.; Smirnov, Valeriy I.

2010-01-01

The enthalpies of solution of ordinary (H 2 O) and heavy (D 2 O) water in nitromethane (NM), acetonitrile (ACN) and propylene carbonate (PC) were measured calorimetrically at 298.15 K. Standard (at the infinite dilution) enthalpies of solution and solvation, along with D 2 O-H 2 O solute isotope effects on the quantities in question, were calculated. The enthalpies of solution of water H/D isotopologues were found to be positive by sign and substantially increasing in magnitude on going from ACN and PC to NM, whereas the corresponding positive solute H/D isotope effect changes in a consequence: NM > ACN > PC. The qualitative interrelations between the enthalpy-isotopic effect of dissolution (solvation) of water and the electron-accepting/donating ability of aprotic dipolar solvent (within a series considered) were found.

Reconstructing lake evaporation history and the isotopic composition of precipitation by a coupled δ18O-δ2H biomarker approach

Science.gov (United States)

Hepp, Johannes; Tuthorn, Mario; Zech, Roland; Mügler, Ines; Schlütz, Frank; Zech, Wolfgang; Zech, Michael

2015-10-01

Over the past decades, δ18O and δ2H analyses of lacustrine sediments became an invaluable tool in paleohydrology and paleolimnology for reconstructing the isotopic composition of past lake water and precipitation. However, based on δ18O or δ2H records alone, it can be challenging to distinguish between changes of the precipitation signal and changes caused by evaporation. Here we propose a coupled δ18O-δ2H biomarker approach that provides the possibility to disentangle between these two factors. The isotopic composition of long chain n-alkanes (n-C25, n-C27, n-C29, n-C31) were analyzed in order to establish a 16 ka Late Glacial and Holocene δ2H record for the sediment archive of Lake Panch Pokhari in High Himalaya, Nepal. The δ2Hn-alkane record generally corroborates a previously established δ18Osugar record reporting on high values characterizing the deglaciation and the Older and the Younger Dryas, and low values characterizing the Bølling and the Allerød periods. Since the investigated n-alkane and sugar biomarkers are considered to be primarily of aquatic origin, they were used to reconstruct the isotopic composition of lake water. The reconstructed deuterium excess of lake water ranges from +57‰ to -85‰ and is shown to serve as proxy for the evaporation history of Lake Panch Pokhari. Lake desiccation during the deglaciation, the Older Dryas and the Younger Dryas is affirmed by a multi-proxy approach using the Hydrogen Index (HI) and the carbon to nitrogen ratio (C/N) as additional proxies for lake sediment organic matter mineralization. Furthermore, the coupled δ18O and δ2H approach allows disentangling the lake water isotopic enrichment from variations of the isotopic composition of precipitation. The reconstructed 16 ka δ18Oprecipitation record of Lake Panch Pokhari is well in agreement with the δ18O records of Chinese speleothems and presumably reflects the Indian Summer Monsoon variability.

Affordable uniform isotope labeling with {sup 2}H, {sup 13}C and {sup 15}N in insect cells

Energy Technology Data Exchange (ETDEWEB)

Sitarska, Agnieszka; Skora, Lukasz; Klopp, Julia; Roest, Susan; Fernández, César; Shrestha, Binesh; Gossert, Alvar D., E-mail: alvar.gossert@novartis.com [Novartis Institutes for BioMedical Research (Switzerland)

2015-06-15

For a wide range of proteins of high interest, the major obstacle for NMR studies is the lack of an affordable eukaryotic expression system for isotope labeling. Here, a simple and affordable protocol is presented to produce uniform labeled proteins in the most prevalent eukaryotic expression system for structural biology, namely Spodoptera frugiperda insect cells. Incorporation levels of 80 % can be achieved for {sup 15}N and {sup 13}C with yields comparable to expression in full media. For {sup 2}H,{sup 15}N and {sup 2}H,{sup 13}C,{sup 15}N labeling, incorporation is only slightly lower with 75 and 73 %, respectively, and yields are typically twofold reduced. The media were optimized for isotope incorporation, reproducibility, simplicity and cost. High isotope incorporation levels for all labeling patterns are achieved by using labeled algal amino acid extracts and exploiting well-known biochemical pathways. The final formulation consists of just five commercially available components, at costs 12-fold lower than labeling media from vendors. The approach was applied to several cytosolic and secreted target proteins.

Stable-isotope geochemistry of the Pierina high-sulfidation Au-Ag deposit, Peru: Influence of hydrodynamics on SO42--H2S sulfur isotopic exchange in magmatic-steam and steam-heated environments

Science.gov (United States)

Fifarek, R.H.; Rye, R.O.

2005-01-01

The Pierina high-sulfidation Au-Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO42--H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (??34S=8.5??? to 31.7???; ??18 OSO4=4.9??? to 16.5???; ??18 OOH=2.2??? to 14.4???; ??D=-97??? to -39???), sulfides (??34 S=-3.0??? to 4.3???), sulfur (??34S=-1.0??? to 1.1???), and clay minerals (??18O=4.3??? to 12.5???; ??D=-126??? to -81???) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration-mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4???6) highly acidic condensate that mixed with meteoric water but retained a magmatic ??34S???S signature of ???1???, (3) SO2 disproportionation to HSO4- and H2S between 320 and 180 ??C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz???alunite-quartz??clay???intermediate argillic???propylitic alteration zoning. Magmatic-steam alunite has higher ??34S (8.5??? to 23.2???) and generally lower ??18OSO4 (1.0 to 11.5???), ??18OOH (-3.4 to 5.9???), and ??D (-93 to -77???) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this

Tracing groundwater recharge sources in the northwestern Indian alluvial aquifer using water isotopes (δ18O, δ2H and 3H)

Science.gov (United States)

Joshi, Suneel Kumar; Rai, Shive Prakash; Sinha, Rajiv; Gupta, Sanjeev; Densmore, Alexander Logan; Rawat, Yadhvir Singh; Shekhar, Shashank

2018-04-01

Rapid groundwater depletion from the northwestern Indian aquifer system in the western Indo-Gangetic basin has raised serious concerns over the sustainability of groundwater and the livelihoods that depend on it. Sustainable management of this aquifer system requires that we understand the sources and rates of groundwater recharge, however, both these parameters are poorly constrained in this region. Here we analyse the isotopic (δ18O, δ2H and tritium) compositions of groundwater, precipitation, river and canal water to identify the recharge sources, zones of recharge, and groundwater flow in the Ghaggar River basin, which lies between the Himalayan-fed Yamuna and Sutlej River systems in northwestern India. Our results reveal that local precipitation is the main source of groundwater recharge. However, depleted δ18O and δ2H signatures at some sites indicate recharge from canal seepage and irrigation return flow. The spatial variability of δ18O, δ2H, d-excess, and tritium reflects limited lateral connectivity due to the heterogeneous and anisotropic nature of the aquifer system in the study area. The variation of tritium concentration with depth suggests that groundwater above c. 80 mbgl is generally modern water. In contrast, water from below c. 80 mbgl is a mixture of modern and old waters, and indicates longer residence time in comparison to groundwater above c. 80 mbgl. Isotopic signatures of δ18O, δ2H and tritium suggest significant vertical recharge down to a depth of 320 mbgl. The spatial and vertical variations of isotopic signature of groundwater reveal two distinct flow patterns in the aquifer system: (i) local flow (above c. 80 mbgl) throughout the study area, and (ii) intermediate and regional flow (below c. 80 mbgl), where water recharges aquifers through large-scale lateral flow as well as vertical infiltration. The understanding of spatial and vertical recharge processes of groundwater in the study area provides important base-line knowledge

Social Analysis Systems (SAS2) - Phase III

International Development Research Centre (IDRC) Digital Library (Canada)

Scaling Up the International Impact of Action Research : Social Analysis ... up the international impact of action research : SAS phase 3; final technical report ... 000 Canadians abroad to work at the local level on various development issues.

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

Predicting trace metal solubility and fractionation in Urban soils from isotopic exchangeability

International Nuclear Information System (INIS)

Mao, L.C.; Young, S.D.; Tye, A.M.; Bailey, E.H.

2017-01-01

Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables. Trace metal reactivity in urban soils depends on both soil properties and the original source material

Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

Science.gov (United States)

Parkin, Gerard

2009-02-17

Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC] (entropy) components opposing each other and having different temperature dependencies. At low temperatures, the ZPE component dominates and the EIE is inverse, while at high temperatures, the [SYM x MMI x EXC] component dominates and the EIE is normal. The inverse nature of the ZPE term is a consequence of the rotational and translational degrees of freedom of RH (R = H, CH(3)) becoming low-energy isotopically sensitive vibrations in the product, while the normal nature of the [SYM x MMI x EXC] component

State Space Modeling Using SAS

Directory of Open Access Journals (Sweden)

Rajesh Selukar

2011-05-01

Full Text Available This article provides a brief introduction to the state space modeling capabilities in SAS, a well-known statistical software system. SAS provides state space modeling in a few different settings. SAS/ETS, the econometric and time series analysis module of the SAS system, contains many procedures that use state space models to analyze univariate and multivariate time series data. In addition, SAS/IML, an interactive matrix language in the SAS system, provides Kalman filtering and smoothing routines for stationary and nonstationary state space models. SAS/IML also provides support for linear algebra and nonlinear function optimization, which makes it a convenient environment for general-purpose state space modeling.

Within-wing isotopic (δ2H, δ13C, δ15N variation of monarch butterflies: implications for studies of migratory origins and diet

Directory of Open Access Journals (Sweden)

Hobson Keith A.

2017-02-01

Full Text Available Increasingly, stable isotope measurements are being used to assign individuals to broad geographic origins based on established relationships between animal tissues and tissue-specific isoscapes. In particular, the eastern North American population of the monarch butterfly (Danaus plexippus has been the subject of several studies using established δ2H and δ13C wingtissue isoscapes to infer natal origins of migrating and overwintering individuals. However, there has been no study investigating potential variance that can derive from subsampling different regions of the wings, especially those regions differing in pigmentation (orange versus black. Within-wing isotopic (δ2H, δ13C, δ15N variance of 40 monarch butterflies collected from natural overwinter mortality on Mexican roost sites were split evenly into two groups: unwashed samples and those washed in a 2:1 chloroform:methanol solvent. Isotopic variance in δ2H and δ13C was related to pigment (within-wing range 5‰ and 0.5‰, respectively, but not region of subsampling. This variance was reduced 3 to 4 fold through solvent washing that removed pigmented surface scales and any adhered oils. Wing δ15N was similarly influenced by pigment (range 0.3‰, but this effect was not reduced through washing. We recommend future isotopic studies of monarchs and other butterflies for migration research to use the same region for subsampling consistently and to wash samples with solvent to reduce isotopic variance related to uncontrolled variance in discrimination (δ2H, δ13C, δ15N and/or adsorbed water vapor (δ2H. These data also need to be included in description of methods.

Auto-inducing media for uniform isotope labeling of proteins with 15N, 13C and 2H

International Nuclear Information System (INIS)

Guthertz, Nicolas; Klopp, Julia; Winterhalter, Aurélie; Fernández, César; Gossert, Alvar D.

2015-01-01

Auto-inducing media for protein expression offer many advantages like robust reproducibility, high yields of soluble protein and much reduced workload. Here, an auto-inducing medium for uniform isotope labelling of proteins with 15 N, 13 C and/or 2 H in E. coli is presented. So far, auto-inducing media have not found widespread application in the NMR field, because of the prohibitively high cost of labeled lactose, which is an essential ingredient of such media. Here, we propose using lactose that is only selectively labeled on the glucose moiety. It can be synthesized from inexpensive and readily available substrates: labeled glucose and unlabeled activated galactose. With this approach, uniformly isotope labeled proteins were expressed in unattended auto-inducing cultures with incorporation of 13 C, 15 N of 96.6 % and 2 H, 15 N of 98.8 %. With the present protocol, the NMR community could profit from the many advantages that auto-inducing media offer

State-to-state dynamics of the H*(n) + HD → D*(n′) + H2 reactive scattering

International Nuclear Information System (INIS)

Yu, Shengrui; Su, Shu; Dai, Dongxu; Yuan, Kaijun; Yang, Xueming

2014-01-01

The state-to-state dynamics of the H * (n) + HD → D * (n ′ ) + H 2 reactive scattering at the collision energy of 0.5 eV have been carried out for the first time by using H-atom Rydberg tagging time-of-flight technique. Experimental results show that the angular distribution of the total H 2 products presents clearly forward-backward asymmetric, which considerably differs from that of the corresponding H + + HD → D + + H 2 reaction predicted by previously theoretical calculations. Such disagreement between these two processes suggests that the Fermi independent-collider model is also not valid in describing the dynamics of isotopic variants of the H * + H 2 reaction. The rotational state distribution of the H 2 products demonstrates a saw-toothed distribution with odd-j ′ > even-j ′ . This interesting observation is strongly influenced by nuclear spin statistics

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

Science.gov (United States)

Qi, Haiping; Coplen, Tyler B.; Gehre, Matthias; Vennemann, Torsten W.; Brand, Willi A.; Geilmann, Heike; Olack, Gerard; Bindeman, Ilya N.; Palandri, Jim; Huang, Li; Longstaffe, Fred J.

2017-01-01

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ2H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ2H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ2H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ2HVSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ2H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are:USGS57 (biotite)δ2HVSMOW-SLAP = − 91.5 ± 2.4 mUr (n = 24)Mass fraction hydrogen = 0.416 ± 0.002% (n = 4)Mass fraction water = 3.74 ± 0.02% (n = 4)USGS58 (muscovite

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

Science.gov (United States)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in

Multi-Isotopic (δ2H, δ13C, δ15N Tracing of Molt Origin for Red-Winged Blackbirds Associated with Agro-Ecosystems.

Directory of Open Access Journals (Sweden)

Scott J Werner

Full Text Available We analyzed stable-hydrogen (δ2H, carbon (δ13C and nitrogen (δ 15N isotope ratios in feathers to better understand the molt origin and food habits of Red-winged Blackbirds (Agelaius phoeniceus near sunflower production in the Upper Midwest and rice production in the Mid-South of the United States. Outer primary feathers were used from 661 after-second-year (ASY male blackbirds collected in Minnesota, Montana, North Dakota and South Dakota (spring collection, and Arkansas, Louisiana, Mississippi, Missouri and Texas (winter collection. The best-fit model indicated that the combination of feather δ2H, δ13C and δ15N best predicted the state of sample collections and thus supported the use of this approach for tracing molt origins in Red-winged Blackbirds. When considering only birds collected in spring, 56% of birds were classified to their collection state on the basis of δ2H and δ13C alone. We then developed feather isoscapes for δ13C based upon these data and for δ2H based upon continental patterns of δ2H in precipitation. We used 81 birds collected at the ten independent sites for model validation. The spatially-explicit assignment of these 81 birds to the δ2H isoscape resulted in relatively high rates (~77% of accurate assignment to collection states. We also modeled the spatial extent of C3 (e.g. rice, sunflower and C4 (corn, millet, sorghum agricultural crops grown throughout the Upper Midwest and Mid-South United States to predict the relative use of C3- versus C4-based foodwebs among sampled blackbirds. Estimates of C3 inputs to diet ranged from 50% in Arkansas to 27% in Minnesota. As a novel contribution to blackbird conservation and management, we demonstrate how such feather isoscapes can be used to predict the molt origin and interstate movements of migratory blackbirds for subsequent investigations of breeding biology (e.g. sex-specific philopatry, agricultural depredation, feeding ecology, physiology of migration and

Multi-Isotopic (δ2H, δ13C, δ15N) Tracing of Molt Origin for Red-Winged Blackbirds Associated with Agro-Ecosystems.

Science.gov (United States)

Werner, Scott J; Hobson, Keith A; Van Wilgenburg, Steven L; Fischer, Justin W

2016-01-01

We analyzed stable-hydrogen (δ2H), carbon (δ13C) and nitrogen (δ 15N) isotope ratios in feathers to better understand the molt origin and food habits of Red-winged Blackbirds (Agelaius phoeniceus) near sunflower production in the Upper Midwest and rice production in the Mid-South of the United States. Outer primary feathers were used from 661 after-second-year (ASY) male blackbirds collected in Minnesota, Montana, North Dakota and South Dakota (spring collection), and Arkansas, Louisiana, Mississippi, Missouri and Texas (winter collection). The best-fit model indicated that the combination of feather δ2H, δ13C and δ15N best predicted the state of sample collections and thus supported the use of this approach for tracing molt origins in Red-winged Blackbirds. When considering only birds collected in spring, 56% of birds were classified to their collection state on the basis of δ2H and δ13C alone. We then developed feather isoscapes for δ13C based upon these data and for δ2H based upon continental patterns of δ2H in precipitation. We used 81 birds collected at the ten independent sites for model validation. The spatially-explicit assignment of these 81 birds to the δ2H isoscape resulted in relatively high rates (~77%) of accurate assignment to collection states. We also modeled the spatial extent of C3 (e.g. rice, sunflower) and C4 (corn, millet, sorghum) agricultural crops grown throughout the Upper Midwest and Mid-South United States to predict the relative use of C3- versus C4-based foodwebs among sampled blackbirds. Estimates of C3 inputs to diet ranged from 50% in Arkansas to 27% in Minnesota. As a novel contribution to blackbird conservation and management, we demonstrate how such feather isoscapes can be used to predict the molt origin and interstate movements of migratory blackbirds for subsequent investigations of breeding biology (e.g. sex-specific philopatry), agricultural depredation, feeding ecology, physiology of migration and sensitivity to

Isotope (δ13C, δ15N, δ2H) diet-tissue discrimination in African grey parrot Psittacus erithacus: implications for forensic studies.

Science.gov (United States)

Symes, Craig; Skhosana, Felix; Butler, Mike; Gardner, Brett; Woodborne, Stephan

2017-12-01

Diet-tissue isotopic relationships established under controlled conditions are informative for determining the dietary sources and geographic provenance of organisms. We analysed δ 13 C, δ 15 N, and non-exchangeable δ 2 H values of captive African grey parrot Psittacus erithacus feathers grown on a fixed mixed-diet and borehole water. Diet-feather Δ 13 C and Δ 15 N discrimination values were +3.8 ± 0.3 ‰ and +6.3 ± 0.7 ‰ respectively; significantly greater than expected. Non-exchangeable δ 2 H feather values (-62.4 ± 6.4 ‰) were more negative than water (-26.1 ± 2.5 ‰) offered during feather growth. There was no positive relationship between the δ 13 C and δ 15 N values of the samples along each feather with the associated samples of food offered, or the feather non-exchangeable hydrogen isotope values with δ 2 H values of water, emphasising the complex processes involved in carbohydrate, protein, and income water routing to feather growth. Understanding the isotopic relationship between diet and feathers may provide greater clarity in the use of stable isotopes in feathers as a tool in determining origins of captive and wild-caught African grey parrots, a species that is widespread in aviculture and faces significant threats to wild populations. We suggest that these isotopic results, determined even in controlled laboratory conditions, be used with caution.

2H isotope effect on 13C chemical shifts of Nitro-Benzo-9-Crown-3

International Nuclear Information System (INIS)

Moghimi, A.; Rastegar, M.; Ghandi, M.; Bijanzadeh, H. R.

2002-01-01

Deuterium substitution on two ortho-substituted-OCH 2 fragments in Nitro-Benzo-9 Crown-3 induces low frequency shifts, positive m ''nΔC j, in all 13 C NMR resonances which is an indication of the increased shielding in this crown ether. The magnitude of these shifts vary from 15 ΔC 7=716 to 54 ΔC 3=15 ppb for C 7 and C 3 carbons directly attached to 2 H, respectively. The influences of concentration and solvent, CDCl 3 CD 3 COCD 3 , and C 6 D 6 , on mn ΔC j values were investigated. The mn ΔC j values depended more on the nature of the solvent than on the concentration. The order of induced isotope shifts is 15 Δ, 51 Δ > 24 Δ, 42 Δ> 34 Δ, 43 Δ > 56 Δ, 65 Δ> 45 Δ, 54 Δ. The isotope shifts observed are suggested to be a sum of contributions from low frequency shift due to inductive-type and negative hyperconjugation perturbations. The C-D bond, as a poorer electron acceptor than a C-H bond induced less positive charge on directly attached oxygens O 1 and O 2. This, in turn, causes shielding of C 1 and C 2 in C1O1CD 2 and C 2 0 2 CD 2 fragments. The difference in 34 ΔC 1 and 43 ΔC 2 values is attributed to the conformational dependence of the negative hyperconjugation. The C 1 and C 2, are in fact, not equally affected by the two CD 2 groups by negative hyperconjugation because of the existence of NO 2 group attached to the benzene ring

Oxygen isotopes and volatile contents of the Gorgona komatiites, Colombia: A confirmation of the deep mantle origin of H2O

Science.gov (United States)

Gurenko, Andrey A.; Kamenetsky, Vadim S.; Kerr, Andrew C.

2016-11-01

We report O isotopes in olivine grains (Fo89-93) and volatile contents (CO2, H2O, F, S, Cl) in olivine-hosted melt inclusions from one Gorgona picrite and five komatiites with the aim of constraining the origin of H2O in these magmas. These samples have previously been analysed for major and trace elements and volatile concentrations (H2O, S, Cl) and B isotopes in melt inclusions. A distinctive feature of the included melts is relatively high contents of volatile components and boron, which show positive anomalies in, otherwise depleted, primitive mantle normalised trace and rare earth element patterns and range in δ11 B from -11.5 to 15.6‰. In this study, the olivines were systematically analysed for O isotopes (1) in the centre of grains, (2) near the grain boundaries and, (3) as close as possible to the studied melt inclusions. The majority of olivines (∼66%) are ;mantle;-like, 4.8 ‰ ≤δ18 O ≤ 5.5 ‰, with a subordinate but still significant number (∼33%) above, and only 2 grains below, this range. There is no systematic difference between the central and marginal parts of the grains. Higher than ;mantle; δ18OOl values are ascribed to low-T (Gorgona mafic and ultramafic magmas.

Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons.

Science.gov (United States)

Muchalski, Hubert; Levonyak, Alexander J; Xu, Libin; Ingold, Keith U; Porter, Ned A

2015-01-14

Hydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.

Synthesis of [methine-3H]DDT and its nitro-analog, and isotope effects in their enzyme-catalyzed dehydrochlorination

International Nuclear Information System (INIS)

Kurihara, N.; Ikemoto, Y.; Okutani, S.; Clark, A.G.

1989-01-01

[methine- 3 H]1,1-Di-(4-chlorophenyl)-2,2,2-trichloroethane ([methine- 3 H]DDT) and its di-(4-nitrophenyl) analog, both of high purity with a moderately high specific activity were prepared. Chloro-benzene was condensed with [1- 3 H]1-(4-chlorophenyl)-2,2,2-trichloro-ethanol, which has been synthesized by sodium boro[ 3 H]hydride reduction of 4-chlorophenyl trichloromethyl ketone. The purified [ 3 H]DDT had a specific activity of 0.77 Ci/mmol (28.49 GBq/mmol). [methine- 3 H]1,1-Diphenyl-2,2,2-trichloroethane was similarly synthesized and was nitrated to give [methine- 3 H]1,1-di-(4-nitrophenyl)-2,2,2-trichloro-ethane of 1.63 Ci/mmol (60.31 GBq/mmol). Dehydrochlorination with housefly enzyme (glutathione-dependent DDT dehydrochlorinase) showed a remarkable isotope effect. For DDT, the observed tritium isotope effect on V max /K m was 11.51±0.52. For the nitro-analog, the value was 11.3±1.2. We measured deuterium isotope effect on V max /K m for DDT in a competitive mode and obtained the value 4.19±0.34. Based on these values, the magnitude of intrinsic isotope effect values on DDT-dehydrochlorination reaction was discussed. (author)

Isotope effects of reactions in quantum solids initiated by IR + UV lasers: quantum model simulations for Cl((2)P(3/2)) + X(2)(ν) → XCl + X in X(2) matrices (X = H, D).

Science.gov (United States)

Korolkov, M V; Manz, J; Schild, A

2010-09-16

, compared to that for reaction 1 . (vi) For a given value of the UV frequency, the translational energy E(trans) increases with mass M(X). Again, this effect supports tunneling of the heavier isotopomer. The isotope effects (i)-(iii), (iv)-(v), and (vi) may be classified as energetic, translational amplitude, and kinematic, respectively. Specifically, the effects (iv)-(v) are due to a systematic decrease of the amplitudes of translational motions of the reactant molecules, from quasi infinite in the gas via still rather large values of para-H(2)(ν) and smaller values for ortho-D(2)(ν) to very small values in classical solids. These isotope effects are special phenomena in quantum solids, which do not occur, neither in the gas phase nor in classical solids. Quantitative predictions, e.g., for the effects of increasing UV frequency on the ratio of reactions probabilities for the UV only versus IR + UV experiments, must account for the interplay of various isotope effects, e.g., (vi) combined with the antagonistic effects (iii) versus (iv) and (v).

SAS2: Guide sur la recherche collaborative et l'engagement social

International Development Research Centre (IDRC) Digital Library (Canada)

À l'encontre de cette façon de voir, les SAS2 favorisent l'« ancrage social » et la ..... les organismes communautaires, les médias, les fondations philanthropiques, ...... Portez attention aux différences qui peuvent influencer la manière dont les ...

Regional origin assignment of red wines from Valencia (Spain) by (2)H NMR and (13)C IRMS stable isotope analysis of fermentative ethanol.

Science.gov (United States)

Giménez-Miralles, J E; Salazar, D M; Solana, I

1999-07-01

The use of the stable hydrogen and carbon isotope ratios of fermentative ethanol as suitable environmental fingerprints for the regional origin identification of red wines from Valencia (Spain) has been explored. Monovarietal Vitis vinifera L. cvs. Bobal, Tempranillo, and Monastrell wines have been investigated by (2)H NMR and (13)C IRMS for the natural ranges of site-specific (2)H/(1)H ratios and global delta(13)C values of ethanol over three vintage years. Statistically significant interregional and interannual (2)H and (13)C abundance differences have been noticed, which are interpreted in terms of environmental and ecophysiological factors of isotope content variation. Multivariate discriminant analysis is shown to provide a convenient means for integration of the classifying information, high discriminating abilities being demonstrated for the (2)H and (13)C fingerprints of ethanol. Reasonable differentiation results are achieved at a microregional scale in terms of geographic provenance and even grapevine genotypic features.

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

Science.gov (United States)

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils

Stable isotope (2H, 17O, 18O) and hydro chemical patterns of precipitation collected in weekly resolution at Hannover, Germany

Science.gov (United States)

Koeniger, Paul; Himmelsbach, Thomas

2016-04-01

Long-term observations of stable isotopes (δ18O and δ2H) in precipitation were initiated in May 2008 at the Federal Institute of Geosciences and Natural Resources (BGR) in Hannover, Germany. In 2014 all precipitation samples were re-analyzed because a purchase of a new laser spectrometer (Picarro L2140-i) now allowed measurements of δ17O and a calculation of the 17O-excess parameter. Starting in October 2015 a routine analysis of hydro chemical parameters was added whenever enough sample aliquot was available (major ions, trace elements). A discussion of the stable isotope data of the seven year series of weekly precipitation samples (n = 370) will be presented. Beneath general patterns (seasonality and trends) we also focus on importance of amount weighing procedures, corrections for minor rain amounts, aspects of sample storage and re-analyzes, as well as impacts through changes in analytical equipment (IRMS, CRD spectroscopy) which is visible from the data. For stable isotopes a Thermo Fisher delta plus IRMS (Gasbench and H-Device) was used until 2011 and from 2012 on a Picarro L2120-i water vapor analyzer with long-term accuracies for quality check samples better than 0.2‰ and 0.8‰ for δ18O and δ2H, respectively.

Eddy Covariance measurements of stable CO2 and H2O isotopologues

Science.gov (United States)

Braden-Behrens, Jelka; Knohl, Alexander

2015-04-01

The analysis of the stable isotope composition of CO2 and H2O fluxes (such as 13C, 18O and 2H in H2O and CO2) has provided valuable insights into ecosystem gas exchange. The approach builds on differences in the isotope signature of different ecosystem components that are primarily caused by the preference for or the discrimination against respective isotope species by important processes within the ecosystem (e.g. photosynthesis or leaf water diffusion). With the ongoing development of laser spectrometric methods, fast and precise measurements of isotopologue mixing ratios became possible, hence also enabling Eddy Covariance (EC) based approaches to directly measure the isotopic composition of CO2 and H2Ov net fluxes on ecosystem scale. During an eight month long measurement campaign in 2015, we plan to simultaneously measure CO2 and H2Ov isotopologue fluxes using an EC approach in a managed beech forest in Thuringia, Germany. For this purpose, we will use two different laser spectrometers for high frequency measurements of isotopic compositions: For H2Ov measurements, we will use an off axis cavity output water vapour isotope analyser (WVIA, Los Gatos Research Inc.) with 5 Hz response; and for CO2 measurements, we will use a quantum cascade laser-based system (QCLAS, Aerodyne Research Inc.) with thermoelectrically cooled detectors and up to 10 Hz measurement capability. The resulting continuous isotopologue flux measurements will be accompanied by intensive sampling campaigns on the leaf scale: Water from leaf, twig, soil and precipitation samples will be analysed in the lab using isotope ratio mass spectrometry. During data analysis we will put a focus on (i) the influence of carbon and oxygen discrimination on the isotopic signature of respective net ecosystem exchange, (ii) on the relationship between evapotranspiration and leaf water enrichment, and (iii) on the 18O exchange between carbon dioxide and water. At present, we already carried out extensive

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

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

OpenAIRE

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

2008-01-01

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the c...

A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction.

Science.gov (United States)

Suleimanov, Yury V; de Tudela, Ricardo Pérez; Jambrina, Pablo G; Castillo, Jesús F; Sáez-Rábanos, Vicente; Manolopoulos, David E; Aoiz, F Javier

2013-03-14

The inclusion of Quantum Mechanical (QM) effects such as zero point energy (ZPE) and tunneling in simulations of chemical reactions, especially in the case of light atom transfer, is an important problem in computational chemistry. In this respect, the hydrogen exchange reaction and its isotopic variants constitute an excellent benchmark for the assessment of approximate QM methods. In particular, the recently developed ring polymer molecular dynamics (RPMD) technique has been demonstrated to give very good results for bimolecular chemical reactions in the gas phase. In this work, we have performed a detailed RPMD study of the H + H(2) reaction and its isotopologues Mu + H(2), D + H(2) and Heμ + H(2), at temperatures ranging from 200 to 1000 K. Thermal rate coefficients and kinetic isotope effects have been computed and compared with exact QM calculations as well as with quasiclassical trajectories and experiment. The agreement with the QM results is good for the heaviest isotopologues, with errors ranging from 15% to 45%, and excellent for Mu + H(2), with errors below 15%. We have seen that RPMD is able to capture the ZPE effect very accurately, a desirable feature of any method based on molecular dynamics. We have also verified Richardson and Althorpe's prediction [J. O. Richardson and S. C. Althorpe, J. Chem. Phys., 2009, 131, 214106] that RPMD will overestimate thermal rates for asymmetric reactions and underestimate them for symmetric reactions in the deep tunneling regime. The ZPE effect along the reaction coordinate must be taken into account when assigning the reaction symmetry in the multidimensional case.

Soil, the orphan hydrological compartment: evidence from O and H stable isotopes?

Science.gov (United States)

Hissler, Christophe; Legout, Arnaud; Barnich, François; Pfister, Laurent

2015-04-01

O and H stable isotopes have been successfully used for decades for studying the exchange of waters between the hydrosphere, the pedosphere and the biosphere. They greatly contribute to improve our understanding of soil-water-plant interactions. In particular, the recent hydrological concept of "two water worlds" (separation of meteoric water that infiltrates the soil as (i) mobile water, which can reach the groundwater and can enter the stream, and as (ii) tightly bound water, which is trapped in the soil microporosity and used by plants) calls for a substantial revision of our perceptual models of runoff generation. Nevertheless, there is a need for testing the applicability of this concept over a large range of ecosystemic contexts (i.e.soil and vegetation types). To date, many investigations have focused on the relationship between the various processes triggering isotope fractionation within soils. So far, the dominating perception is that the isotope profile of water observed in soils is solely due to evaporative fractionation and its shape is dependent on climate and soil parameters. However, as of today the influence of biogeochemical processes on the spatio-temporal variability of δ18O and δD of the soil solutions has been rarely quantified. O and H exchanges between soil water and other soil compartments (living organisms, minerals, exchange capacity, organic matter) remain poorly known and require deeper investigations. Eventually, we need to better understand the distribution of O and H isotopes throughout the soil matrix. In order to address these issues, we have designed and carried out two complementary isotope experiments that use one liter soil columns of a 2mm-sieved and air-dried soil. Our objectives were (1) to observe the temporal evolution of the water O and H isotopic composition starting from the field capacity to the complete drying of the soil and (2) to determine the impact of soil biogeochemical properties on the isotopic composition

Tree-ring C-H-O isotope variability and sampling

International Nuclear Information System (INIS)

Leavitt, Steven W.

2010-01-01

In light of the proliferation of tree-ring isotope studies, the magnitude and cause of variability of tree-ring δ 13 C, δ 18 O and δ 2 H within individual trees (circumferential) and among trees at a site is examined in reference to field and laboratory sampling requirements and strategies. Within this framework, this paper provides a state-of-knowledge summary of the influence of 'juvenile' isotope effects, ageing effects, and genetic effects, as well as the interchangeability of species, choice of ring segment to analyze (whole ring, earlywood or latewood), and the option of sample pooling. The range of isotopic composition of the same ring among trees at a site is ca. 1-3 per mille for δ 13 C, 1-4 per mille δ 18 O, and 5-30 per mille for δ 2 H, whereas the circumferential variability within a tree is lower. A standard prescription for sampling and analysis does not exist because of differences in field environmental circumstances and mixed findings represented in relevant published literature. Decisions in this regard will usually be tightly constrained by goals of the study and project resources. Sampling 4-6 trees at a site while avoiding juvenile effects in rings near the pith seems to be the most commonly used methodology, and although there are some reasoned arguments for analyzing only latewood and developing separate isotope records from each tree, the existence of some contradictory findings together with efforts to reduce cost and effort have prompted alternate strategies (e.g., most years pooled with occasional analysis of rings in the sequence separately for each tree) that have produced useful results in many studies.

Assessment of insulin action in insulin-dependent diabetes mellitus using [6(14)C]glucose, [3(3)H]glucose, and [2(3)H]glucose. Differences in the apparent pattern of insulin resistance depending on the isotope used

International Nuclear Information System (INIS)

Bell, P.M.; Firth, R.G.; Rizza, R.A.

1986-01-01

To determine whether [2(3)H], [3(3)H], and [6(14)C]glucose provide an equivalent assessment of glucose turnover in insulin-dependent diabetes mellitus (IDDM) and nondiabetic man, glucose utilization rates were measured using a simultaneous infusion of these isotopes before and during hyperinsulinemic euglycemic clamps. In the nondiabetic subjects, glucose turnover rates determined with [6(14)C]glucose during insulin infusion were lower (P less than 0.02) than those determined with [2(3)H]glucose and higher (P less than 0.01) than those determined with [3(3)H]glucose. In IDDM, glucose turnover rates measured with [6(14)C]glucose during insulin infusion were lower (P less than 0.05) than those determined with [2(3)H]glucose, but were not different from those determined with [3(3)H]glucose. All three isotopes indicated the presence of insulin resistance. However, using [3(3)H]glucose led to the erroneous conclusion that glucose utilization was not significantly decreased at high insulin concentrations in the diabetic patients. [6(14)C] and [3(3)H]glucose but not [2(3)H]glucose indicated impairment in insulin-induced suppression of glucose production. These results indicate that tritiated isotopes do not necessarily equally reflect the pattern of glucose metabolism in diabetic and nondiabetic man

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer, Sfax, southeastern Tunisia

Science.gov (United States)

Ayadi, Rahma; Trabelsi, Rim; Zouari, Kamel; Saibi, Hakim; Itoi, Ryuichi; Khanfir, Hafedh

2017-12-01

Major element concentrations and stable (δ18O and δ2H) and radiogenic (3H and 14C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water-rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ18O and δ2H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO4 and Ca-Na-Cl-SO4. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ18O and δ2H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

Comparison of ArcGIS and SAS Geostatistical Analyst to Estimate Population-Weighted Monthly Temperature for US Counties.

Science.gov (United States)

Xiaopeng, Q I; Liang, Wei; Barker, Laurie; Lekiachvili, Akaki; Xingyou, Zhang

Temperature changes are known to have significant impacts on human health. Accurate estimates of population-weighted average monthly air temperature for US counties are needed to evaluate temperature's association with health behaviours and disease, which are sampled or reported at the county level and measured on a monthly-or 30-day-basis. Most reported temperature estimates were calculated using ArcGIS, relatively few used SAS. We compared the performance of geostatistical models to estimate population-weighted average temperature in each month for counties in 48 states using ArcGIS v9.3 and SAS v 9.2 on a CITGO platform. Monthly average temperature for Jan-Dec 2007 and elevation from 5435 weather stations were used to estimate the temperature at county population centroids. County estimates were produced with elevation as a covariate. Performance of models was assessed by comparing adjusted R 2 , mean squared error, root mean squared error, and processing time. Prediction accuracy for split validation was above 90% for 11 months in ArcGIS and all 12 months in SAS. Cokriging in SAS achieved higher prediction accuracy and lower estimation bias as compared to cokriging in ArcGIS. County-level estimates produced by both packages were positively correlated (adjusted R 2 range=0.95 to 0.99); accuracy and precision improved with elevation as a covariate. Both methods from ArcGIS and SAS are reliable for U.S. county-level temperature estimates; However, ArcGIS's merits in spatial data pre-processing and processing time may be important considerations for software selection, especially for multi-year or multi-state projects.

Cross-cultural adaptation of the Sport Anxiety Scale-2 (SAS-2 for the Brazilian context

Directory of Open Access Journals (Sweden)

Viviane Vedovato Silva-Rocha

Full Text Available Abstract Objective To present the process of cross-cultural adaptation of the Sport Anxiety Scale-2 (SAS-2 for the Brazilian context. Method The following stages were used: translation into Brazilian Portuguese by independent translators, elaboration of a synthesis version, back-translation, evaluation by experts and pretest with target population. Results All the stages of cross-cultural adaptation were completed, and in the majority of items evaluated, good concordance between experts was obtained (≥ 80%. Suggested adjustments were compiled into the consensus version by the two authors, with the resulting material being considered adequate in the pretest (and thus no further changes were needed. Termed as “Escala de Ansiedade Esportiva-2,” the final version was considered by the main author of the original scale as an official version in Brazilian Portuguese. Conclusions In view of the fulfilment of all steps suggested for the cross-cultural adaptation process, the SAS-2 is now available in Brazilian Portuguese to be tested for its psychometric qualities.

Synthesis and spectroscopic stereospecificity assay of the deuterated quinolizidine alkaloids (2S)-[2H]- and (2R)-[2H]-sparteine

International Nuclear Information System (INIS)

Ebner, T.; Meese, C.O.; Rebell, J.

1989-01-01

Borohydride reduction of the (+)-1,2-dehydrosparteinium salts proceeds almost exclusively from the Si side, yielding, respectively, the stereoselectively (2S)(β)-deuterated (-)-sparteine and the (2R)(α)-deuterated (-)-sparteine. Stereo-chemistry and isotopic purity of the deuterium label (≥98%) are established unequivocally by 1 H, 2 H and 13 C NMR spectroscopy. (author)

Isotope effects in aqueous systems. Excess thermodynamic properties of 1,3-dimethylurea solutions in H2O and D2O

International Nuclear Information System (INIS)

Jakli, G.; Hook, W.A. Van

1997-01-01

The osmotic coefficients of 1,3-dimethylurea-h 2 (DMUh 2 )/H 2 O and 1,3-dimethylurea-d 2 (DMUd 2 )/D 2 O solutions (1, 2, 4, 12, and 20 m aq , 15 < t/degree C < 80) were obtained from differential vapor pressure measurements. Excess partial molar free energies, enthalpies, and entropies for the solvent and their isotope effects were calculated from the temperature derivatives of the osmotic coefficients. New partial molar volume data are reported at 25 C at low and intermediate concentrations. The thermodynamic properties of solution are compared with those of urea and discussed using the cage model of hydrophobic hydration. The results support the mixed (polar-apolar) character of this compound and show that its structural effect on water changes with temperature and concentration

Conducting Meta-Analysis Using SAS

CERN Document Server

Arthur, Winfried; Huffcutt, Allen I; Arthur, Winfred

2001-01-01

Conducting Meta-Analysis Using SAS reviews the meta-analysis statistical procedure and shows the reader how to conduct one using SAS. It presents and illustrates the use of the PROC MEANS procedure in SAS to perform the data computations called for by the two most commonly used meta-analytic procedures, the Hunter & Schmidt and Glassian approaches. This book serves as both an operational guide and user's manual by describing and explaining the meta-analysis procedures and then presenting the appropriate SAS program code for computing the pertinent statistics. The practical, step-by-step instru

Cross sections of the O++H2→OH++H ion-molecule reaction and isotopic variants (D2, HD): Quasiclassical trajectory study and comparison with experiments

International Nuclear Information System (INIS)

Martinez, Rodrigo; Sierra, Jose Daniel; Gonzalez, Miguel

2005-01-01

A dynamics study [cross section and microscopic mechanism versus collision energy (E T )] of the reaction O + +H 2 →OH + +H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D 2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E T =0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E T , and considering the influence of the collinear [OHH] + absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies

Isotope effect in the organic superconductor β_H-(BEDT-TTF)2I3 where BEDT-TTF is bis (ethylenedithiotetrathiafulvalene)

Science.gov (United States)

Auban-Senzier, P.; Bourbonnais, C.; Jérome, D.; Lenoir, C.; Batail, P.; Canadell, E.; Buisson, J. P.; Lefrant, S.

1993-03-01

We have performed the simultaneous investigation of the isotope effect on the superconducting transition and on the Raman spectra in the organic superconductor β_H-(BEDT-TTF)2I3 (T_c = 8 K). For this purpose, we substitute ^{13}C for ^{12}C on the carbon sites of the central double bond of BEDT-TTF molecule. The isotope shifts measured by Raman experiments can be fairly well explained by standard molecular dynamics. However, the critical temperature is lowered by 0.2 K in the ^{13}C enriched material. We analyse the possible sources of this remarkable downward shift which leads to an isotope coefficient higher than the BCS value. The extended-Hückel calculations of the density of states for the two HOMO bands of β_H-(BEDT-TTF)2I3 do show that, within the framework of a weak coupling theory, its sizeable variation on the scale of ω_D cannot account for the observed isotope effect. On the other hand, we discuss how inelastic electronic scattering observed in resistivity measurements just above T_c can lead through a pair breaking mechanism to a sizeable increase of the isotope coefficient. Nous présentons une étude simultanée d'effet isotopique sur la transition supraconductrice et les spectres Raman dans le supraconducteur organique β_H-(BEDT-TTF)2I3 (T_c = 8 K). Pour cela, nous avons synthétisé le composé dans lequel les atomes de carbone de la double liaison centrale de la molécule BEDT-TTF sont substitués par l'isotope ^{13}C. Les déplacements isotopiques mesurés par spectroscopie Raman sont bien expliqués par la dynamique moléculaire standard. Cependant, la température critique est abaissée de 0.2 K dans le matériau enrichi en ^{13}C. Nous étudions les origines possibles de cet effet qui permet d'obtenir un coefficient isotopique supérieur à la valeur BCS. Des calculs de la densité d'états effectués par la méthode de Hückel étendue pour les deux bandes HOMO du composé montrent que, dans le cadre d'une théorie de couplage faible

Time dependent quantum dynamics study of the O++H2(v=0,j=0)→OH++H ion-molecule reaction and isotopic variants (D2,HD)

International Nuclear Information System (INIS)

Martinez, Rodrigo; Sierra, Jose Daniel; Gray, Stephen K.; Gonzalez, Miguel

2006-01-01

The time dependent real wave packet method using the helicity decoupling approximation was used to calculate the cross section evolution with collision energy (excitation function) of the O + +H 2 (v=0,j=0)→OH + +H reaction and its isotopic variants with D 2 and HD, using the best available ab initio analytical potential energy surface. The comparison of the calculated excitation functions with exact quantum results and experimental data showed that the present quantum dynamics approach is a very useful tool for the study of the selected and related systems, in a quite wide collision energy interval (approximately 0.0-1.1 eV), involving a much lower computational cost than the quantum exact methods and without a significant loss of accuracy in the cross sections

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

Science.gov (United States)

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

SASWeave: Literate Programming Using SAS

Directory of Open Access Journals (Sweden)

Russell V. Lenth

2007-05-01

Full Text Available SASweave is a collection of scripts that allow one to embed SAS code into a LATEX document, and automatically incorporate the results as well. SASweave is patterned after Sweave, which does the same thing for code written in R. In fact, a document may contain both SAS and R code. Besides the convenience of being able to easily incorporate SAS examples in a document, SASweave facilitates the concept of “literate programming”: having code, documentation, and results packaged together. Among other things, this helps to ensure that the SAS output in the document is in concordance with the code.

SASWeave: Literate Programming Using SAS

DEFF Research Database (Denmark)

Lenth, Russell V; Højsgaard, Søren

2007-01-01

SASweave is a collection of scripts that allow one to embed SAS code into a LATEX document, and automatically incorporate the results as well. SASweave is patterned after Sweave, which does the same thing for code written in R. In fact, a document may contain both SAS and R code. Besides...... the convenience of being able to easily incorporate SAS examples in a document, SASweave facilitates the concept of "literate programming": having code, documentation, and results packaged together. Among other things, this helps to ensure that the SAS output in the document is in concordance with the code...

Determination of Isotopic Abundance of 2H, 13C, 18O, and 37Cl in Biofield Energy Treated Dichlorophenol Isomers

OpenAIRE

Branton, Alice; Trivedi, Dahryn; Nayak, Gopal; Trivedi, Mahendra; Saikia, Gunin; Jana, Snehasis

2016-01-01

2,4-Dichlorophenol (2,4-DCP) and 2,6-dichlorophenol (2,6-DCP) are two isomers of dichlorophenols, have been used as preservative agents for wood, paints, vegetable fibers and as intermediates in the production of pharmaceuticals and dyes. The aim of the study was to evaluate the impact of biofield energy treatment on the isotopic abundance ratios of 2H/1H or 13C/12C, and 18O/16O or 37Cl/35Cl, in dichlorophenol isomers using gas chromatography-mass spectrometry (GC-MS). The 2,4-DCP and 2,6-DCP...

Application and validation of isotope dilution method (IDM) for predicting bioavailability of hydrophobic organic contaminants in soil.

Science.gov (United States)

Wang, Jie; Taylor, Allison; Schlenk, Daniel; Gan, Jay

2018-05-01

Risk assessment of hydrophobic organic contaminants (HOCs) using the total chemical concentration following exhaustive extraction may overestimate the actual availability of HOCs to non-target organisms. Existing methods for estimating HOC bioavailability in soil have various operational limitations. In this study, we explored the application of isotope dilution method (IDM) to quantify the accessible fraction (E) of DDTs and PCBs in both historically-contaminated and freshly-spiked soils. After addition of 13 C or deuterated analogues to a soil sample, the phase distribution of isotope-labeled and native chemicals reached an apparent equilibrium within 48 h of mixing. The derived E values in the three soils ranged from 0.19 to 0.82, depending on the soil properties and also the contact time of HOCs (i.e., aging). The isotope dilution method consistently predicted greater accumulation into earthworm (Eisenia fetida) than that by polyethylene (PE) or solid phase microextraction (SPME) sampler, likely because desorption in the gut enhanced bioavailability of soil-borne HOCs. A highly significant linear regression (R 2  = 0.91) was found between IDM and 24-h Tenax desorption, with a slope statistically identical to 1. The IDM-derived accessible concentration (C e ) was further shown to accurately predict tissue residues in earthworm exposed in the same soils. Given the relatively short duration and simple steps, IDM has the potential to be readily adopted for measuring HOC bioaccessibility in soil and for improving risk assessment and evaluation of remediation efficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantum-tunneling isotope-exchange reaction H2+D-→HD +H-

Science.gov (United States)

Yuen, Chi Hong; Ayouz, Mehdi; Endres, Eric S.; Lakhamanskaya, Olga; Wester, Roland; Kokoouline, Viatcheslav

2018-02-01

The tunneling reaction H2+D-→HD +H- was studied in a recent experimental work at low temperatures (10, 19, and 23 K) by Endres et al. [Phys. Rev. A 95, 022706 (2017), 10.1103/PhysRevA.95.022706]. An upper limit of the rate coefficient was found to be about 10-18cm3 /s. In the present study, reaction probabilities are determined using the ABC program developed by Skouteris et al. [Comput. Phys. Commun. 133, 128 (2000), 10.1016/S0010-4655(00)00167-3]. The probabilities for ortho-H2 and para-H2 in their ground rovibrational states are obtained numerically at collision energies above 50 meV with the total angular momentum J =0 -15 and extrapolated below 50 meV using a WKB approach. Thermally averaged rate coefficients for ortho- and para-H2 are obtained; the largest one, for ortho-H2, is about 3.1 ×10-20cm3 /s, which agrees with the experimental results.

Some measurements of H/D polarizability isotope effects using differential refractometry

Energy Technology Data Exchange (ETDEWEB)

Foster Smith, M; Van Hook, W A [Tennessee Univ., Knoxville (USA). Dept. of Chemistry

1989-05-01

Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.).

Some measurements of H/D polarizability isotope effects using differential refractometry

International Nuclear Information System (INIS)

Foster Smith, M.; Van Hook, W.A.

1989-01-01

Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.)

Investigating Unsaturated Zone Travel Times with Tritium and Stable Isotopes

Science.gov (United States)

Visser, A.; Thaw, M.; Van der Velde, Y.

2017-12-01

Travel times in the unsaturated zone are notoriously difficult to assess. Travel time tracers relying on the conservative transport of dissolved (noble) gases (tritium-helium, CFCs or SF6) are not applicable. Large water volume requirements of other cosmogenic radioactive isotopes (sulfur-35, sodium-22) preclude application in the unsaturated zone. Prior investigations have relied on models, introduced tracers, profiles of stable isotopes or tritium, or a combination of these techniques. Significant unsaturated zone travel times (UZTT) complicate the interpretation of stream water travel time tracers by ranked StorAge Selection (rSAS) functions. Close examination of rSAS functions in a sloping soil lysimeter[1] show the effect of the UZTT on the shape of the rSAS cumulative distribution function. We studied the UZTT at the Southern Sierra Critical Zone Observatory (SS-CZO) using profiles of tritium and stable isotopes (18O and 2H) in the unsaturated zone, supported by soil water content data. Tritium analyses require 100-500 mL of soil water and therefore large soil samples (1-5L), and elaborate laboratory procedures (oven drying, degassing and noble gas mass spectrometry). The high seasonal and interannual variability in precipitation of the Mediterranean climate, variable snow pack and high annual ET/P ratios lead to a dynamic hydrology in the deep unsaturated soils and regolith and highly variable travel time distributions. Variability of the tritium concentration in precipitation further complicates direct age estimates. Observed tritium profiles (>3 m deep) are interpreted in terms of advective and dispersive vertical transport of the input variability and radioactive decay of tritium. Significant unsaturated zone travel times corroborate previously observed low activities of short-lived cosmogenic radioactive nuclides in stream water. Under these conditions, incorporating the UZTT is critical to adequately reconstruct stream water travel time distributions. 1

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

Science.gov (United States)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in

The evaluation of isotopic composition for TRIGA 14 MW spent fuel

International Nuclear Information System (INIS)

Covaci, St.; Toma, C.; Preda, M.

2008-01-01

In the summer of 1999 year, a first shipment of TRIGA HEU spent fuel to INEEL U.S.A. has taken place. he TRIGA HEU fuel was burned in the TRIGA steady state 14 MW reactor between 1980 and 1996 years. At the moment of prepared documentation for the shipment (July 1999), the evaluation of isotopic composition was calculated with ORIGEN-2 code with an irradiation history adequately prepared. Subsequently (May - June 2000), the evaluation was repeated with SAS2H module of SCALE 4.4a system. In the paper the results and the comparisons of the codes are presented, and the accuracy and convenient application of SCALE 4.4a system are emphasized. (authors)

Auto-inducing media for uniform isotope labeling of proteins with {sup 15}N, {sup 13}C and {sup 2}H

Energy Technology Data Exchange (ETDEWEB)

Guthertz, Nicolas [Institute of Cancer Research, Division of Structural Biology (United Kingdom); Klopp, Julia; Winterhalter, Aurélie; Fernández, César; Gossert, Alvar D., E-mail: alvar.gossert@novartis.com [Novartis Institutes for BioMedical Research (Switzerland)

2015-06-15

Auto-inducing media for protein expression offer many advantages like robust reproducibility, high yields of soluble protein and much reduced workload. Here, an auto-inducing medium for uniform isotope labelling of proteins with {sup 15}N, {sup 13}C and/or {sup 2}H in E. coli is presented. So far, auto-inducing media have not found widespread application in the NMR field, because of the prohibitively high cost of labeled lactose, which is an essential ingredient of such media. Here, we propose using lactose that is only selectively labeled on the glucose moiety. It can be synthesized from inexpensive and readily available substrates: labeled glucose and unlabeled activated galactose. With this approach, uniformly isotope labeled proteins were expressed in unattended auto-inducing cultures with incorporation of {sup 13}C, {sup 15}N of 96.6 % and {sup 2}H, {sup 15}N of 98.8 %. With the present protocol, the NMR community could profit from the many advantages that auto-inducing media offer.

Synthesis and spectroscopic stereospecificity assay of the deuterated quinolizidine alkaloids (2S)-( sup 2 H)- and (2R)-( sup 2 H)-sparteine

Energy Technology Data Exchange (ETDEWEB)

Ebner, T.; Meese, C.O. (Fischer-Bosch Inst. fuer Klinische Pharmakologie, Stuttgart (Germany, F.R.)); Rebell, J. (Stuttgart Univ. (Germany, F.R.). Inst. fuer Organische Chemie); Fischer, P. (Stuttgart Univ. (Germany, F.R.). Inst. fuer Organische Chemie Fischer-Bosch Inst. fuer Klinische Pharmakologie, Stuttgart (Germany, F.R.))

1989-04-01

Borohydride reduction of the (+)-1,2-dehydrosparteinium salts proceeds almost exclusively from the Si side, yielding, respectively, the stereoselectively (2S)({beta})-deuterated (-)-sparteine and the (2R)({alpha})-deuterated (-)-sparteine. Stereo-chemistry and isotopic purity of the deuterium label ({>=}98%) are established unequivocally by {sup 1}H, {sup 2}H and {sup 13}C NMR spectroscopy. (author).

CRC DEPLETION CALCULATIONS FOR THE NON-RODDED ASSEMBLIES IN BATCHES 8 AND 9 CRYSTAL RIVER UNIT 3

International Nuclear Information System (INIS)

Wilson, Michael L.

2001-01-01

The purpose of this design analysis is to document the SAS2H depletion calculations of certain non-rodded fuel assemblies from batches 8 and 9 of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for Commercial Reactor Critical (CRC) evaluations to support the development of the disposal criticality methodology. A non-rodded assembly is one which never contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) during its irradiation history. The objective of this analysis is to provide SAS2H generated isotopic compositions for each fuel assembly's depleted fuel and depleted burnable poison materials. These SAS2H generated isotopic compositions are acceptable for use in CRC benchmark reactivity calculations containing the various fuel assemblies

CRC DEPLETION CALCULATIONS FOR THE NON-RODDED ASSEMBLIES IN BATCHES 4 AND 5 OF CRYSTAL RIVER UNIT 3

International Nuclear Information System (INIS)

Wright, Kenneth D.

1997-01-01

The purpose of this design analysis is to document the SAS2H depletion calculations of certain non-rodded fuel assemblies from batches 4 and 5 of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for commercial Reactor Critical (CRC) evaluations to support the development of the disposal criticality methodology. A non-rodded assembly is one which never contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) during its irradiation history. The objective of this analysis is to provide SAS2H generated isotopic compositions for each fuel assembly's depleted fuel and depleted burnable poison materials. These SAS2H generated isotopic compositions are acceptable for use in CRC benchmark reactivity calculations containing the various fuel assemblies

Correlation between precipitation and geographical location of the δ2H values of the fatty acids in milk and bulk milk powder

Science.gov (United States)

Ehtesham, E.; Baisden, W. T.; Keller, E. D.; Hayman, A. R.; Van Hale, R.; Frew, R. D.

2013-06-01

Hydrogen isotope ratios (δ2H) have become a tool for food traceability and authentication of agricultural products. The principle is that the isotopic composition of the produce is influenced by environmental and biological factors and hence exhibits a spatial differentiation of δ2H. This study investigates the variation in δ2H values of New Zealand milk, both in the bulk powder and individual fatty acids extracted from milk samples from dairy factories across New Zealand. Multivariate statistical analyses were used to test for relationships between δ2H of bulk milk powder, milk fatty acid and geographical location. Milk powder samples from different regions of New Zealand were found to exhibit patterns in isotopic composition similar to the corresponding regional precipitation associated with their origin. A model of δ2H in precipitation was developed based on measurements between 2007 and 2010 at 51 stations across New Zealand (Frew and Van Hale, 2011). The model uses multiple linear regressions to predict daily δ2H from 2 geographic and 5 rain-weighted climate variables from the 5 × 5 km New Zealand Virtual Climate Station Network (VCSN). To approximate collection radius for a drying facility the modelled values were aggregated within a 50 km radius of each dairy factory and compared to observed δ2H values of precipitation and bulk milk powder. Daily δ2H predictions for the period from August to December for the area surrounding the sample collection sites were highly correlated with the δ2H values of bulk milk powder. Therefore the δ2H value of milk fatty acids demonstrates promise as a tool for determining the provenance of milk powders and products where milk powder is an ingredient. Separation of milk powder origin to geographic sub-regions within New Zealand was achieved. Hydrogen isotope measurements could be used to complement traditional tracking systems in verifying point of origin.

State-to-state dynamics of the H{sup *}(n) + HD → D{sup *}(n{sup ′}) + H{sub 2} reactive scattering

Energy Technology Data Exchange (ETDEWEB)

Yu, Shengrui; Su, Shu; Dai, Dongxu; Yuan, Kaijun, E-mail: kjyuan@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn; Yang, Xueming, E-mail: kjyuan@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (China)

2014-01-21

The state-to-state dynamics of the H{sup *}(n) + HD → D{sup *}(n{sup ′}) + H{sub 2} reactive scattering at the collision energy of 0.5 eV have been carried out for the first time by using H-atom Rydberg tagging time-of-flight technique. Experimental results show that the angular distribution of the total H{sub 2} products presents clearly forward-backward asymmetric, which considerably differs from that of the corresponding H{sup +} + HD → D{sup +} + H{sub 2} reaction predicted by previously theoretical calculations. Such disagreement between these two processes suggests that the Fermi independent-collider model is also not valid in describing the dynamics of isotopic variants of the H{sup *} + H{sub 2} reaction. The rotational state distribution of the H{sub 2} products demonstrates a saw-toothed distribution with odd-j{sup ′} > even-j{sup ′}. This interesting observation is strongly influenced by nuclear spin statistics.

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Science.gov (United States)

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

2014-01-01

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Badcock, C.C.; Hwang, W.C.; Kalsch, J.F.

1978-09-29

Chemical kinetic modeling studies of vibrational-photochemical isotope enrichment have been performed on two systems: Model (I), H/sup 79/Br(H/sup 81/Br) + Cl/sub 2/ and, Model (II), H/sup 37/Cl(H/sup 35/Cl) + Br. Pulsed laser excitation was modeled to the first excited vibrational level of H/sup 79/Br in Model I and the first and second excited vibrational levels of both HCl isotopes in Model II. These are prototype systems of exoergic (Model I) and endoergic (Model II) reactions. The effects on enrichment of varying the external parameters (pressure, laser intensity) and the internal parameters (rate constants for V-V exchange and excited-state reactions) were examined. Studies of these prototype systems indicate that a favorable reaction for enrichment, with isotopically-specific excitation and a significantly accelerated vibrationally-excited-state reaction should have the following properties: the reaction from v = 0 should be only moderately exoergic, and the most favorable coreactant should be a polyatomic species, such as alkyl radical. Direct excitation of the reacting vibrational level is at least an order of magnitude more favorable for enrichment than is population by energy transfer. Enrichment of the minor isotope by these processes is more effective than is major isotope enrichment. Within limits, increased laser intensity is beneficial. However, for sequential excitation of a second vibrational level, major isotope enrichment can be diminished by high populations of the first vibrational level.

Application of natural isotopes ("1"8O, "2H and "1"4C) to study the dynamics of ground water in connection with river water in Bandung area

International Nuclear Information System (INIS)

Evarista Ristin Pujiindiyati and Satrio

2013-01-01

Water table in the center of Bandung basin has been decreased around 1-2 m/year since 1990 whereas in the slope has been decreased at higher level of 15 m. Water level decreasing are going to increase continuously because of increasing number of deep wells (>40 m). In 1970, there were 96 deep wells which have been registered, but now number of deep wells is estimated of more than 4700. Therefore, a study of interrelationship between groundwater and surface water, and determination of recharge area for Bandung basin are crucial research to be conducted. Stable isotopes in nature such as "2H and "1"8O, and radioactive isotope of "1"4C can give important information about groundwater dynamic pattern. In this research, 24 deep groundwater samples, 28 shallow groundwater and river water samples (Citarum, Cikapundung, Cikeruh and Citarik rivers) and shallow groundwater along the rivers were collected. Results from plotting δ"1"8O and δ"2H showed that most of shallow groundwater did not relate to river water except three locations, they are Loteng Sumbersari and Bojong Mas groundwater near to Citarum river, and groundwater near to Cikapundung river. Isotope "1"4C analysis indicated that deep groundwater of Bandung basin did not show relationship either by shallow groundwater or river water. Its iso-age line contour determined that dynamic pattern of deep groundwater in Bandung basin comes from northern and southern hills to direction of north-west area such that both areas are suggested as conservation zone. Rate of deep groundwater movement predicted from iso-age contour is around 0.25 to 3 m/year. (author)

Isotopic dependences of the dielectric strength of gases: new observations, classification, and possible origins

International Nuclear Information System (INIS)

Christophorou, L.G.; Rodrigo, H.; Marode, E.; Bastien, F.

1985-01-01

In this paper we report: (1) the finding that the CH 4 /CD 4 nonuniform field behavior is polarity dependent (i.e., the V/sub s/ of CD 4 is lower than the V/sub s/ of CH 4 for negative polarity which is just the opposite of that observed for positive polarity); (2) discuss the origins of the observed isotope effects and predict new isotopic dependences of V/sub s/; and (3) report results on the V/sub s/ of H 2 S and D 2 S for negative polarity which confirm their predicted isotopic behavior

Adaptive beamforming for low frequency SAS imagery and bathymetry

NARCIS (Netherlands)

Hayes, M.P.; Hunter, A.J.

2012-01-01

Synthetic aperture side-scan sonar (SAS) is a mature technology for high-resolution sea floor imaging [1]. Interferometric synthetic aperture sonars (InSAS) use additional hydrophones in a vertical array for bathymetric mapping [2]. This has created high-resolution bathymetry in deep water

Melatonin labeled with hydrogen isotopes

International Nuclear Information System (INIS)

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

1989-01-01

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

Melatonin labelled by hydrogen isotopes

International Nuclear Information System (INIS)

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

1988-01-01

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

Predictive isotopic biogeochemistry of lipids from the Black Sea and Cariaco Trench

International Nuclear Information System (INIS)

Freeman, K.H.; Hayes, J.M.; Wakeham, S.G.

1991-01-01

Carbon isotopic compositions of autotrophic organisms can be predicted based on recently established relationships between [CO 2 (aq)] and var-epsilon p , the isotopic fractionation accompanying carbon fixation. In both the Black Sea and the Cariaco Trench, where [CO 2 (aq)] values are known and δ values for hydrocarbons were recently determined, predicted biomass δ values can be compared to those of biomarkers extracted from POM and sediment samples. The agreement is good, although a 5 per-thousand range in δ values is observed for the lipids, which may be due to ecological factors or to contributions from organisms that assimilate HCO 3 -. Lycopane and pentamethyleicosane apparently derive from planktonic organisms. Diploptene in the Black Sea apparently is derived from chemoautotrophic bacteria living at the oxic/anoxic interface. Some odd-C, long-chain n-alkanes have planktonic δ values, and the authors suggest they are not strict terrestrial indicators

Protective effect of Dendrobium officinale polysaccharides on H2O2-induced injury in H9c2 cardiomyocytes.

Science.gov (United States)

Zhao, Xiaoyan; Dou, Mengmeng; Zhang, Zhihao; Zhang, Duoduo; Huang, Chengzhi

2017-10-01

The preliminary studies have shown that Dendrobium officinale possessed therapeutic effects on hypertension and atherosclerosis. Studies also reported that Dendrobium officinale polysaccharides showed antioxidant capabilities. However, little is known about its effects on myocardial cells under oxidative stress. The present study was designed to study the protective effect of Dendrobium officinale polysaccharides against H 2 O 2 -induced oxidative stress in H9c2 cells. MTT assay was carried out to determine the cell viability of H9c2 cells when pretreated with Dendrobium officinale polysaccharides. Fluorescent microscopy measurements were performed for evaluating the apoptosis in H9c2 cells. Furthermore, effects of Dendrobium officinale polysaccharides on the activities of antioxidative indicators (malondialdehyde, superoxide dismutase), reactive oxygen species (ROS) production and mitochondrial membrane potential (MMP) levels were analyzed. Dendrobium officinale polysaccharides attenuated H 2 O 2 -induced cell death, as determined by the MTT assay. Dendrobium officinale polysaccharides decreased malondialdehyde levels, increased superoxide dismutase activities, and inhibited the generation of intracellular ROS. Moreover, pretreatment with Dendrobium officinale polysaccharides also inhibited apoptosis and increased the MMP levels in H9c2 cells. These results suggested the protective effects of Dendrobium officinale polysaccharides against H 2 O 2 -induced injury in H9c2 cells. The results also indicated the anti-oxidative capability of Dendrobium officinale polysaccharides. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Comparison between IRMS and CRDS methods in the determination of isotopic ratios 2H/1H and 18O/16O in water

International Nuclear Information System (INIS)

Santos, T. H. R.; Zucchi, M. R.; Lemaire, T.; Azevedo, A. E. G.

2013-01-01

Traditionally, the method used for measuring the isotope ratios is the Isotope Ratio Mass Spectrometers (IRMS). A new method has been used to determine the isotopic abundances, the Cavity Ring-Down Spectroscopy (CRDS). It consists of a technique of direct absorption, of high sensitivity, which is based on measuring the absorption ratio, as a function of time, of the light confined in a high finesse optical cavity, instead of the magnitude of light beam absorption. The values of 18 O/ 16 O and D/H ratios are determined with respect to international standards VSMOW, GISP and SLAP from the International Atomic Energy Agency (IAEA). In this work, the IRMS and CRDS techniques are compared, verifying that the CRDS technique is promising and has some advantages compared to IRMS. It uses a smaller amount of sample, the isotope measurements are made simultaneously from the steam, reducing the analysis time. It also shows good reproducibility and accuracy, and it does not require a preliminary sample preparation.

2 H-fractionations during the biosynthesis of carbohydrates and lipids imprint a metabolic signal on the δ2 H values of plant organic compounds.

Science.gov (United States)

Cormier, Marc-André; Werner, Roland A; Sauer, Peter E; Gröcke, Darren R; Leuenberger, Markus C; Wieloch, Thomas; Schleucher, Jürgen; Kahmen, Ansgar

2018-04-01

Hydrogen (H) isotope ratio (δ 2 H) analyses of plant organic compounds have been applied to assess ecohydrological processes in the environment despite a large part of the δ 2 H variability observed in plant compounds not being fully elucidated. We present a conceptual biochemical model based on empirical H isotope data that we generated in two complementary experiments that clarifies a large part of the unexplained variability in the δ 2 H values of plant organic compounds. The experiments demonstrate that information recorded in the δ 2 H values of plant organic compounds goes beyond hydrological signals and can also contain important information on the carbon and energy metabolism of plants. Our model explains where 2 H-fractionations occur in the biosynthesis of plant organic compounds and how these 2 H-fractionations are tightly coupled to a plant's carbon and energy metabolism. Our model also provides a mechanistic basis to introduce H isotopes in plant organic compounds as a new metabolic proxy for the carbon and energy metabolism of plants and ecosystems. Such a new metabolic proxy has the potential to be applied in a broad range of disciplines, including plant and ecosystem physiology, biogeochemistry and palaeoecology. © 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.

CRC DEPLETION CALCULATIONS FOR THE NON-RODDED ASSEMBLIES IN BATCHES 4 AND 5 OF CRYSTAL RIVER UNIT 3

Energy Technology Data Exchange (ETDEWEB)

Kenneth D. Wright

1997-07-30

The purpose of this design analysis is to document the SAS2H depletion calculations of certain non-rodded fuel assemblies from batches 4 and 5 of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for commercial Reactor Critical (CRC) evaluations to support the development of the disposal criticality methodology. A non-rodded assembly is one which never contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) during its irradiation history. The objective of this analysis is to provide SAS2H generated isotopic compositions for each fuel assembly's depleted fuel and depleted burnable poison materials. These SAS2H generated isotopic compositions are acceptable for use in CRC benchmark reactivity calculations containing the various fuel assemblies.

Modelling the Spatial Isotope Variability of Precipitation in Syria

Energy Technology Data Exchange (ETDEWEB)

Kattan, Z.; Kattaa, B. [Department of Geology, Atomic Energy Commission of Syria (AECS), Damascus (Syrian Arab Republic)

2013-07-15

Attempts were made to model the spatial variability of environmental isotope ({sup 18}O, {sup 2}H and {sup 3}H) compositions of precipitation in syria. Rainfall samples periodically collected on a monthly basis from 16 different stations were used for processing and demonstrating the spatial distributions of these isotopes, together with those of deuterium excess (d) values. Mathematically, the modelling process was based on applying simple polynomial models that take into consideration the effects of major geographic factors (Lon.E., Lat.N., and altitude). The modelling results of spatial distribution of stable isotopes ({sup 18}O and {sup 2}H) were generally good, as shown from the high correlation coefficients (R{sup 2} = 0.7-0.8), calculated between the observed and predicted values. In the case of deuterium excess and tritium distributions, the results were most likely approximates (R{sup 2} = 0.5-0.6). Improving the simulation of spatial isotope variability probably requires the incorporation of other local meteorological factors, such as relative air humidity, precipitation amount and vapour pressure, which are supposed to play an important role in such an arid country. (author)

THE MAGNESIUM ISOTOPOLOGUES OF MgH IN THE A 2Π-X 2Σ+ SYSTEM

International Nuclear Information System (INIS)

Hinkle, Kenneth H.; Wallace, Lloyd; Ram, Ram S.; Bernath, Peter F.; Sneden, Christopher; Lucatello, Sara

2013-01-01

Using laboratory hollow cathode spectra we have identified lines of the less common magnesium isotopologues of MgH, 25 MgH and 26 MgH, in the A 2 Π-X 2 Σ + system. Based on the previous analysis of 24 MgH, molecular lines have been measured and molecular constants derived for 25 MgH and 26 MgH. Term values and linelists, in both wavenumber and wavelength units, are presented. The A 2 Π-X 2 Σ + system of MgH is important for measuring the magnesium isotope ratios in stars. Examples of analysis using the new linelists to derive the Mg isotope ratio in a metal poor dwarf and giant are shown

Zeolite encapsulation of H2

International Nuclear Information System (INIS)

Cooper, S.; Lakner, J.F.

1982-08-01

Experiments with H 2 have shown that it is possible to encapsulate gases in the structure of certain molecular sieves. This method may offer a better means of temporarily storing and disposing of tritium over some others presently in use. The method may also prove safer, and may enable isotope separation, and removal of 3 He. Initial experiments were performed with H 2 to screen potential candidates for use with tritium

Long-Term Precipitation Isotope Ratios (δ18O, δ2H, d-excess) in the Northeast US Reflect Atlantic Ocean Warming and Shifts in Moisture Sources

Science.gov (United States)

Puntsag, T.; Welker, J. M.; Mitchell, M. J.; Klein, E. S.; Campbell, J. L.; Likens, G.

2014-12-01

The global water cycle is exhibiting dramatic changes as global temperatures increase resulting in increases in: drought extremes, flooding, alterations in storm track patterns with protracted winter storms, and greater precipitation variability. The mechanisms driving these changes can be difficult to assess, but the spatial and temporal patterns of precipitation water isotopes (δ18O, δ2H, d-excess) provide a means to help understand these water cycle changes. However, extended temporal records of isotope ratios in precipitation are infrequent, especially in the US. In our study we analyzed precipitation isotope ratio data from the Hubbard Brook Experimental Forest in New Hampshire that has the longest US precipitation isotope record, to determine: 1) the monthly composited averages and trends from 1967 to 2012 (45 years); ; 2) the relationships between abiotic properties such as local temperatures, precipitation type, storm tracks and isotope ratio changes; and 3) the influence of regional shifts in moisture sources and/or changes in N Atlantic Ocean water conditions on isotope values. The seasonal variability of Hubbard Brook precipitation isotope ratios is consistent with other studies, as average δ18O values are ~ -15‰ in January and ~ -5 ‰ in July. However, over the 45 year record there is a depletion trend in the δ 18O values (becoming isotopically lighter with a greater proportion of 16O), which coupled with less change in δ 2H leads to increases in d-excess values from ~ -10‰ around 1970 to greater than 10‰ in 2009. These changes occurred during a period of warming as opposed to cooling local temperatures indicating other processes besides temperature are controlling long-term water isotope traits in this region. We have evidence that these changes in precipitation isotope traits are controlled in large part by an increases in moisture being sourced from a warming N Atlantic Ocean that is providing evaporated, isotopically

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

Science.gov (United States)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

Radiochemical studies of neutron deficient actinide isotopes

International Nuclear Information System (INIS)

Williams, K.E.

1978-04-01

The production of neutron deficient actinide isotopes in heavy ion reactions was studied using alpha, gamma, x-ray, and spontaneous fission detection systems. A new isotope of berkelium, 242 Bk, was produced with a cross-section of approximately 10 μb in reactions of boron on uranium and nitrogen on thorium. It decays by electron capture with a half-life of 7.0 +- 1.3 minutes. The alpha-branching ratio for this isotope is less than 1% and the spontaneous fission ratio is less than 0.03%. Studies of (Heavy Ion, pxn) and (Heavy Ion, αxn) transfer reactions in comparison with (Heavy ion, xn) compound nucleus reactions revealed transfer reaction cross-sections equal to or greater than the compound nucleus yields. The data show that in some cases the yield of an isotope produced via a (H.I.,pxn) or (H.I.,αxn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z 1 + Z 2 = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,αxn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of 228 Pu, 230 Pu, 232 Cm, or 238 Cf was observed indicating that strictly empirical extrapolations of spontaneous fission half-life data is inadequate for predictions of half-lives for unknown neutron deficient actinide isotopes

Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

Science.gov (United States)

Jørgensen, Niels; Banoeng-Yakubo, Bruce

2001-03-01

Analyses of environmental isotopes (18O, 2H, and 87Sr/86Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The 87Sr/86Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of 18O and 2H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Résumé. L'analyse des isotopes du milieu (18O, 2H, et 87Sr/86Sr) a été mise en œuvre pour des études hydrogéologiques portant sur des eaux souterraines salées des aquifères du bassin de Keta (Ghana). Les rapports isotopiques 87Sr/86Sr de l'eau souterraine et de l'eau de surface du bassin de Keta reflètent principalement la géologie et la composition minéralogique des formations des bassins d'alimentation et des zones de recharge. Les compositions isotopiques en 18O et en 2H des eaux souterraines profondes présentent de faibles variations et se placent près de la droite des eaux météoriques mondiales. Les eaux des nappes peu profondes

Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

Science.gov (United States)

Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

2015-05-27

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

Science.gov (United States)

Preston, Tom

2014-01-01

This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

CRC DEPLETION CALCULATIONS FOR THE RODDED ASSEMBLIES IN BATCHES 1, 2, 3, AND 1X OF CRYSTAL RIVER UNIT 3

Energy Technology Data Exchange (ETDEWEB)

Kenneth D. Wright

1997-09-03

The purpose of this design analysis is to document the SAS2H depletion calculations of certain rodded fuel assemblies from batches 1, 2, 3, and 1X of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for Commercial Reactor Critical (CRC) evaluations to support the development of the disposal criticality methodology. A rodded assembly is one that contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) for some period of time during its irradiation history. The objective of this analysis is to provide SAS2H calculated isotopic compositions of depleted fuel and depleted burnable poison for each fuel assembly to be used in subsequent CRC reactivity calculations containing the fuel assemblies.

CRC DEPLETION CALCULATIONS FOR THE RODDED ASSEMBLIES IN BATCHES 1, 2, 3, AND 1X OF CRYSTAL RIVER UNIT 3

International Nuclear Information System (INIS)

Wright, Kenneth D.

1997-01-01

The purpose of this design analysis is to document the SAS2H depletion calculations of certain rodded fuel assemblies from batches 1, 2, 3, and 1X of the Crystal River Unit 3 pressurized water reactor (PWR) that are required for Commercial Reactor Critical (CRC) evaluations to support the development of the disposal criticality methodology. A rodded assembly is one that contains a control rod assembly (CRA) or an axial power shaping rod assembly (APSRA) for some period of time during its irradiation history. The objective of this analysis is to provide SAS2H calculated isotopic compositions of depleted fuel and depleted burnable poison for each fuel assembly to be used in subsequent CRC reactivity calculations containing the fuel assemblies

Preparation of Pt-SDB hydrophobic catalyst used in H2-H2O isotope exchange reaction

International Nuclear Information System (INIS)

Li Junhua; Kang Yi; Ruan Hao; Dou Qincheng; Han Yande; Hu Shilin

2001-01-01

The preparation of Pt-SDB hydrophobic catalyst is studied, in which platinum as active metal and polystyrene divinylbenzene (SDB) as the carrier. Hydrogen isotope exchange reaction is carried out with Pt-SDB catalyst in counter-current in the trickle bed. The effect of preparing condition on the activity of catalyst is discussed. The results show that the excellent catalyst is obtained by reduced at the temperature of 200 degree C over 8 hours. Hydrophobic catalyst is high activity and stability as the amount of platinum content is 3%, the platinum can reach the economic use with the content of (1-2)%

Tritium isotopic exchange in air detritiation dryers

International Nuclear Information System (INIS)

Everatt, A.E.; Johnson, R.E.; Senohrabek, J.A.; Shultz, C.M.

1989-02-01

Isotopic exchange between tritiated and non-tritiated water species in a molecular sieve bed has been demonstrated. At high humidities (+6 degrees Celsius dew point) the rate of tritium isotopic exchange in a 2.4 L molecular sieve bed has been demonstrated to be at least 50% of published exchange rates. In an industrial-sized air detritiation dryer, utilizing the pretreatment technique of H 2 O steam washing to elute the residual tritium, a DF of 12 600 has been demonstrated when operating at an inlet vapor tritium concentration of 14 Ci/kg and at inlet and outlet dew points of 4.8 and -54 degrees Celsius, respectively. In the NPD dryer bed studied, which was not optimally designed for full benefit from isotopic exchange, at least one order of magnitude in additional detritiation is attributed to isotopic exchange in the unsaturated zone. The technique of eluting the residual tritium from an industrial sized bed by H 2 O washing at high temperature, high humidity and low bed loading has been demonstrated to be a fast and effective way of removing tritium from a molecular sieve bed during regeneration. The isotopic exchange model accurately predicted the exchange between tritiated and non-tritiated water species in a molecular sieve bed where there is no net adsorption or desorption. The model's prediction of the tritium breakthrough trend observed in the NPD tests was poor; however, a forced fit can be achieved if the exchange rates in the MTZ and the unsaturated zone are manipulated. More experiments are needed to determine the relative rates of tritium exchange in the saturated, mass transfer, and unsaturated zones of a dryer bed

Applications of stable isotopes of 2H, 13C and 15N to clinical problems

International Nuclear Information System (INIS)

Klein, P.D.; Szczepanik, P.A.; Hachey, D.L.

1974-01-01

The function of the Argonne Program is to provide synthetic, analytical instrumental capability in a core facility for the clinical investigator who needs to use 2 H, 13 C, or 15 N labelled compounds for metabolic or clinical research on pregnant women, newborn infants, young children, or for mass screening. To carry out such application development, there were six stages which were recurrent steps in every application. Five fundamental strategies should be adopted to establish the use of stable isotopes in clinical work. The instrument required for measurements was a combined gas chromatograph-mass spectrometer, and its use was schematically illustrated. Some of the successful experiences with compounds labelled by stable isotopes, such as deuterium labelled chenodeoxycholic acid, and respective 13 C and 15 N-labelled glycine were described. Deutrium labelled bile acid enabled easy and safe determination of the size of the bile acid pool and the replacement rate, providing clearer diagnoses for cholestatic liver disease and gallstones. 13 C and 15 N labelled compounds were used in clinical studies, of children with genetic disorders of amino acid metabolism, i.e., non ketotic hyperflycinemia, B 12 -responsive methyl malonic acidemia, and Lesch-Nyhan syndrome. 15 N-labelled glycine was also studied in a child with Lesch-Nyhan syndrome. (Mukohata, S.)

Synergistic effect of the simultaneous chemometric analysis of {sup 1}H NMR spectroscopic and stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data: Application to wine analysis

Energy Technology Data Exchange (ETDEWEB)

Monakhova, Yulia B., E-mail: yul-monakhova@mail.ru [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Department of Chemistry, Saratov State University, Astrakhanskaya Street 83, Saratov 410012 (Russian Federation); Godelmann, Rolf [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Hermann, Armin [Landesuntersuchungsamt -Institut für Lebensmittelchemie und Arzneimittelprüfung, Emy-Roeder-Straße 1, Mainz 55129 (Germany); Kuballa, Thomas [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Cannet, Claire; Schäfer, Hartmut; Spraul, Manfred [Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Rutledge, Douglas N. [AgroParisTech, UMR 1145, Ingénierie Procédés Aliments, 16 rue Claude Bernard, Paris F-75005 (France)

2014-06-23

Highlights: • {sup 1}H NMR profilings of 718 wines were fused with stable isotope analysis data (SNIF-NMR, {sup 18}O, {sup 13}C). • The best improvement was obtained for prediction of the geographical origin of wine. • Certain enhancement was also obtained for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data). • Independent component analysis was used as an alternative chemometric tool for classification. - Abstract: It is known that {sup 1}H NMR spectroscopy represents a good tool for predicting the grape variety, the geographical origin, and the year of vintage of wine. In the present study we have shown that classification models can be improved when {sup 1}H NMR profiles are fused with stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data. Variable selection based on clustering of latent variables was performed on {sup 1}H NMR data. Afterwards, the combined data of 718 wine samples from Germany were analyzed using linear discriminant analysis (LDA), partial least squares-discriminant analysis (PLS-DA), factorial discriminant analysis (FDA) and independent components analysis (ICA). Moreover, several specialized multiblock methods (common components and specific weights analysis (ComDim), consensus PCA and consensus PLS-DA) were applied to the data. The best improvement in comparison with {sup 1}H NMR data was obtained for prediction of the geographical origin (up to 100% for the fused data, whereas stable isotope data resulted only in 60–70% correct prediction and {sup 1}H NMR data alone in 82–89% respectively). Certain enhancement was obtained also for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data), whereas in case of grape varieties improved models were not obtained. The combination of {sup 1}H NMR data with stable isotope data improves efficiency of classification models for geographical origin and vintage of wine and can be potentially used for other food products as well.

Hydrogenation and Deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} on Cold Grains: A Clue to the Formation Mechanism of C{sub 2}H{sub 6} with Astronomical Interest

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, Hitomi; Kawakita, Hideyo [Koyama Astronomical Observatory, Kyoto Sangyo University Motoyama, Kamigamo, Kita-ku, Kyoto 603-8555 (Japan); Hidaka, Hiroshi; Hama, Tetsuya; Watanabe, Naoki [Institute of Low Temperature Science, Hokkaido University N19-W8, Kita-ku, Sapporo, Hokkaido 060-0819 (Japan); Lamberts, Thanja; Kästner, Johannes, E-mail: h_kobayashi@kyoto-nijikoubou.com [Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)

2017-03-10

We quantitatively investigated the hydrogen addition reactions of acetylene (C{sub 2}H{sub 2}) and ethylene (C{sub 2}H{sub 4}) on amorphous solid water (ASW) at 10 and 20 K relevant to the formation of ethane (C{sub 2}H{sub 6}) on interstellar icy grains. We found that the ASW surface enhances the reaction rates for C{sub 2}H{sub 2} and C{sub 2}H{sub 4} by approximately a factor of 2 compared to those on the pure-solid C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, probably due to an increase in the sticking coefficient and adsorption energy of the H atoms on ASW. In contrast to the previous proposal that the hydrogenation rate of C{sub 2}H{sub 4} is orders of magnitude larger than that of C{sub 2}H{sub 2}, the present results show that the difference in hydrogenation rates of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} is only within a factor of 3 on both the surfaces of pure solids and ASW. In addition, we found the small kinetic isotope effect for hydrogenation/deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, despite the requirement of quantum tunneling. At 20 K, the reaction rate of deuteration becomes even larger than that of hydrogenation. These unusual isotope effects might originate from a slightly larger number density of D atoms than H atoms on ASW at 20 K. The hydrogenation of C{sub 2}H{sub 2} is four times faster than CO hydrogenation and can produce C{sub 2}H{sub 6} efficiently through C{sub 2}H{sub 4} even in the environment of a dark molecular cloud.

Predictions and Verification of an Isotope Marine Boundary Layer Model

Science.gov (United States)

Feng, X.; Posmentier, E. S.; Sonder, L. J.; Fan, N.

2017-12-01

A one-dimensional (1D), steady state isotope marine boundary layer (IMBL) model is constructed. The model includes meteorologically important features absent in Craig and Gordon type models, namely height-dependent diffusion/mixing and convergence of subsiding external air. Kinetic isotopic fractionation results from this height-dependent diffusion which starts as pure molecular diffusion at the air-water interface and increases linearly with height due to turbulent mixing. The convergence permits dry, isotopically depleted air subsiding adjacent to the model column to mix into ambient air. In δD-δ18O space, the model results fill a quadrilateral, of which three sides represent 1) vapor in equilibrium with various sea surface temperatures (SSTs) (high d18O boundary of quadrilateral); 2) mixture of vapor in equilibrium with seawater and vapor in the subsiding air (lower boundary depleted in both D and 18O); and 3) vapor that has experienced the maximum possible kinetic fractionation (high δD upper boundary). The results can be plotted in d-excess vs. δ18O space, indicating that these processes all cause variations in d-excess of MBL vapor. In particular, due to relatively high d-excess in the descending air, mixing of this air into the MBL causes an increase in d-excess, even without kinetic isotope fractionation. The model is tested by comparison with seven datasets of marine vapor isotopic ratios, with excellent correspondence; >95% of observational data fall within the quadrilateral area predicted by the model. The distribution of observations also highlights the significant influence of vapor from the nearby converging descending air on isotopic variations in the MBL. At least three factors may explain the affect the isotopic composition of precipitation. The model can be applied to modern as well as paleo- climate conditions.

Statistical data analysis using SAS intermediate statistical methods

CERN Document Server

Marasinghe, Mervyn G

2018-01-01

The aim of this textbook (previously titled SAS for Data Analytics) is to teach the use of SAS for statistical analysis of data for advanced undergraduate and graduate students in statistics, data science, and disciplines involving analyzing data. The book begins with an introduction beyond the basics of SAS, illustrated with non-trivial, real-world, worked examples. It proceeds to SAS programming and applications, SAS graphics, statistical analysis of regression models, analysis of variance models, analysis of variance with random and mixed effects models, and then takes the discussion beyond regression and analysis of variance to conclude. Pedagogically, the authors introduce theory and methodological basis topic by topic, present a problem as an application, followed by a SAS analysis of the data provided and a discussion of results. The text focuses on applied statistical problems and methods. Key features include: end of chapter exercises, downloadable SAS code and data sets, and advanced material suitab...

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

Science.gov (United States)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

Linking Isotopes and Panmixia: High Within-Colony Variation in Feather δ2H, δ13C, and δ15N across the Range of the American White Pelican.

Directory of Open Access Journals (Sweden)

Matthew W Reudink

Full Text Available Complete panmixia across the entire range of a species is a relatively rare phenomenon; however, this pattern may be found in species that have limited philopatry and frequent dispersal. American white pelicans (Pelecanus erythrorhyncos provide a unique opportunity to examine the role of long-distance dispersal in facilitating gene flow in a species recently reported as panmictic across its broad breeding range. This species is also undergoing a range expansion, with new colonies arising hundreds of kilometers outside previous range boundaries. In this study, we use a multiple stable isotope (δ2H, δ13C, δ15N approach to examine feather isotopic structuring at 19 pelican colonies across North America, with the goal of establishing an isotopic basemap that could be used for assigning individuals at newly established breeding sites to source colonies. Within-colony isotopic variation was extremely high, exceeding 100‰ in δ2H within some colonies (with relatively high variation also observed for δ13C and δ15N. The high degree of within-site variation greatly limited the utility of assignment-based approaches (42% cross-validation success rate; range: 0-90% success. Furthermore, clustering algorithms identified four likely isotopic clusters; however, those clusters were generally unrelated to geographic location. Taken together, the high degree of within-site isotopic variation and lack of geographically-defined isotopic clusters preclude the establishment of an isotopic basemap for American white pelicans, but may indicate that a high incidence of long-distance dispersal is facilitating gene flow, leading to genetic panmixia.

Radiochemical studies of neutron deficient actinide isotopes

Energy Technology Data Exchange (ETDEWEB)

Williams, K.E.

1978-04-01

The production of neutron deficient actinide isotopes in heavy ion reactions was studied using alpha, gamma, x-ray, and spontaneous fission detection systems. A new isotope of berkelium, /sup 242/Bk, was produced with a cross-section of approximately 10 ..mu..b in reactions of boron on uranium and nitrogen on thorium. It decays by electron capture with a half-life of 7.0 +- 1.3 minutes. The alpha-branching ratio for this isotope is less than 1% and the spontaneous fission ratio is less than 0.03%. Studies of (Heavy Ion, pxn) and (Heavy Ion, ..cap alpha..xn) transfer reactions in comparison with (Heavy ion, xn) compound nucleus reactions revealed transfer reaction cross-sections equal to or greater than the compound nucleus yields. The data show that in some cases the yield of an isotope produced via a (H.I.,pxn) or (H.I.,..cap alpha..xn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z/sub 1/ + Z/sub 2/ = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,..cap alpha..xn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of /sup 228/Pu, /sup 230/Pu, /sup 232/Cm, or /sup 238/Cf was observed indicating that strictly empirical extrapolations of spontaneous fission half-life data is inadequate for predictions of half-lives for unknown neutron deficient actinide isotopes.

Land-use change effects on fluxes and isotopic composition of CO2 and CH4 in Panama, and possible insights into the atmospheric H2 cycle

Science.gov (United States)

Pendall, E.; Schwendenmann, L.; Potvin, C.

2003-12-01

Land-use changes in tropical regions are believed to release a quantity of C to the atmosphere which is similar in magnitude to the entire "missing" sink for anthropogenic CO2. Our research attempts to evaluate carbon cycling in three land-cover systems in central Panama: cow pasture, native tree plantation, and undisturbed moist forest. In this ongoing project, we are collecting samples of air from profiles in the stable, nocturnal boundary layer, which is dominated by ecosystem respiration. Samples are analyzed for CO2 and its isotopes, CH4 and its C isotopic composition, N2O, H2, CO, and SF6. We use a flux-gradient method to estimate ecosystem-scale fluxes of trace gases from soil to the atmosphere. Keeling plot intercepts reflect the respiratory contribution of C3 and C4 biomass under contrasting land cover systems, and how this varies with pronounced wet-dry seasonal cycles. C isotopes of methane and gradients of molecular hydrogen provide insight into the source of methane production from pasture and plantation soils. Rainforest soils, in contrast, are sinks for both atmospheric methane and hydrogen. The process oriented nature of this field experiment will contribute to parameterization of carbon cycle models at a variety of spatial scales.

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

Science.gov (United States)

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

2010-02-24

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

Inferring the source of evaporated waters using stable H and O isotopes

Science.gov (United States)

Stable isotope ratios of H and O are widely used to identify the source of water, e.g., in aquifers, river runoff, soils, plant xylem, and plant-based beverages. In situations where the sampled water is partially evaporated, its isotope values will have evolved along an evaporati...

Fitting polytomous Rasch models in SAS

DEFF Research Database (Denmark)

Christensen, Karl Bang

2006-01-01

The item parameters of a polytomous Rasch model can be estimated using marginal and conditional approaches. This paper describes how this can be done in SAS (V8.2) for three item parameter estimation procedures: marginal maximum likelihood estimation, conditional maximum likelihood estimation, an...

The synthesis of 7-chloro-5-pentadeuteriophenyl-1-methyl-1H-1, 5-benzodiazepine-2,4(3H, 5H)dione ([2H5]clobazam)

International Nuclear Information System (INIS)

Borel, A.G.; Abbott, F.S.

1990-01-01

Pentadeuteriophenyl clobazam was synthesized in essentially quantitative isotopic purity, and characterized by 1 H-NMR and mass spectroscopy. The title compound was found to be >98% pure by HPLC, and its retention time (t R 6.17 min) was less than that of an authentic clobazam standard (t R 6.32 min). Of the five steps in the synthesis of clobazam, the most susceptible to deuterium exchange was the nucleophilic substitution of 2,4-dichloronitrobenzene by aniline-d 7 to form N-(5-chloro-2-nitrophenyl)penta-deuteriophenylamine. In this step, the isotopic impurity aniline-2,3,4,5-d 5 introduced protons from nitrogen into the ortho and para positions of the deuteriophenyl ring of N-(5-chloro-2-nitrophenyl)pentadeuteriophenylamine. (author)

Isotopic ratios D/H and 15N/14N in giant planets

Science.gov (United States)

Marboeuf, Ulysse; Thiabaud, Amaury; Alibert, Yann; Benz, Willy

2018-04-01

The determination of isotopic ratios in planets is important since it allows us to investigate the origins and initial composition of materials. The present work aims to determine the possible range of values for isotopic ratios D/H and 15N/14N in giant planets. The main objective is to provide valuable theoretical assumptions on the isotopic composition of giant planets, their internal structure, and the main reservoirs of species. We use models of ice formation and planet formation that compute the composition of ices and gas accreted in the core and the envelope of planets. Assuming a single initial value for isotopic ratios in volatile species, and disruption of planetesimals in the envelope of gaseous planets, we obtain a wide variety of D/H and 15N/14N ratios in low-mass planets (≤100 Mearth) due to the migration pathway of planets, the accretion time of gas species whose relative abundance evolves with time, and isotope exchanges among species. If giant planets with mass greater than 100 Mearth have solar isotopic ratios such as Jupiter and Saturn due to their higher envelope mass, Neptune-type planets present values ranging between one and three times the solar value. It seems therefore difficult to use isotopic ratios in the envelope of these planets to get information about their formation in the disc. For giant planets, the ratios allow us to constrain the mass fraction of volatile species in the envelope needed to reproduce the observational data by assuming initial values for isotopic ratios in volatile species.

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

Energy Technology Data Exchange (ETDEWEB)

Rustad, James R.; Zarzycki, Piotr

2008-07-29

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

Human-Induced Long-Term Shifts in Gull Diet from Marine to Terrestrial Sources in North America's Coastal Pacific: More Evidence from More Isotopes (δ2H, δ34S).

Science.gov (United States)

Hobson, Keith A; Blight, Louise K; Arcese, Peter

2015-09-15

Measurements of naturally occurring stable isotopes in tissues of seabirds and their prey are a powerful tool for investigating long-term changes in marine foodwebs. Recent isotopic (δ(15)N, δ(13)C) evidence from feathers of Glaucous-winged Gulls (Larus glaucescens) has shown that over the last 150 years, this species shifted from a midtrophic marine diet to one including lower trophic marine prey and/or more terrestrial or freshwater foods. However, long-term isotopic patterns of δ(15)N and δ(13)C cannot distinguish between the relative importance of lower trophic-level marine foods and terrestrial sources. We examined 48 feather stable-hydrogen (δ(2)H) and -sulfur (δ(34)S) isotope values from this same 150-year feather set and found additional isotopic evidence supporting the hypothesis that gulls shifted to terrestrial and/or freshwater prey. Mean feather δ(2)H and δ(34)S values (± SD) declined from the earliest period (1860-1915; n = 12) from -2.5 ± 21.4 ‰ and 18.9 ± 2.7 ‰, respectively, to -35.5 ± 15.5 ‰ and 14.8 ± 2.4 ‰, respectively, for the period 1980-2009 (n = 12). We estimated a shift of ∼ 30% increase in dependence on terrestrial/freshwater sources. These results are consistent with the hypothesis that gulls increased terrestrial food inputs in response to declining forage fish availability.

Defining an absolute reference frame for 'clumped' isotope studies of CO 2

Science.gov (United States)

Dennis, Kate J.; Affek, Hagit P.; Passey, Benjamin H.; Schrag, Daniel P.; Eiler, John M.

2011-11-01

We present a revised approach for standardizing and reporting analyses of multiply substituted isotopologues of CO 2 (i.e., 'clumped' isotopic species, especially the mass-47 isotopologues). Our approach standardizes such data to an absolute reference frame based on theoretical predictions of the abundances of multiply-substituted isotopologues in gaseous CO 2 at thermodynamic equilibrium. This reference frame is preferred over an inter-laboratory calibration of carbonates because it enables all laboratories measuring mass 47 CO 2 to use a common scale that is tied directly to theoretical predictions of clumping in CO 2, regardless of the laboratory's primary research field (carbonate thermometry or CO 2 biogeochemistry); it explicitly accounts for mass spectrometric artifacts rather than convolving (and potentially confusing) them with chemical fractionations associated with sample preparation; and it is based on a thermodynamic equilibrium that can be experimentally established in any suitably equipped laboratory using commonly available materials. By analyzing CO 2 gases that have been subjected to established laboratory procedures known to promote isotopic equilibrium (i.e., heated gases and water-equilibrated CO 2), and by reference to thermodynamic predictions of equilibrium isotopic distributions, it is possible to construct an empirical transfer function that is applicable to data with unknown clumped isotope signatures. This transfer function empirically accounts for the fragmentation and recombination reactions that occur in electron impact ionization sources and other mass spectrometric artifacts. We describe the protocol necessary to construct such a reference frame, the method for converting gases with unknown clumped isotope compositions to this reference frame, and suggest a protocol for ensuring that all reported isotopic compositions (e.g., Δ 47 values; Eiler and Schauble, 2004; Eiler, 2007) can be compared among different laboratories and

Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

International Nuclear Information System (INIS)

Vickridge, I.C.; Ganem, J.-J.; Battistig, G.; Szilagyi, E.

2000-01-01

The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in 18 O. Measurement of the 18 O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in 18 O(p,α) 15 N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in 16 O 2 , is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar

Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

Energy Technology Data Exchange (ETDEWEB)

Vickridge, I.C. E-mail: vickridge@gps.jussieu.fr; Ganem, J.-J.; Battistig, G.; Szilagyi, E

2000-03-01

The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in {sup 18}O. Measurement of the {sup 18}O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in {sup 18}O(p,{alpha}){sup 15}N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in {sup 16}O{sub 2}, is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar.

Criticality reference benchmark calculations for burnup credit using spent fuel isotopics

International Nuclear Information System (INIS)

Bowman, S.M.

1991-04-01

To date, criticality analyses performed in support of the certification of spent fuel casks in the United States do not take credit for the reactivity reduction that results from burnup. By taking credit for the fuel burnup, commonly referred to as ''burnup credit,'' the fuel loading capacity of these casks can be increased. One of the difficulties in implementing burnup credit in criticality analyses is that there have been no critical experiments performed with spent fuel which can be used for computer code validation. In lieu of that, a reference problem set of fresh fuel critical experiments which model various conditions typical of light water reactor (LWR) transportation and storage casks has been identified and used in the validation of SCALE-4. This report documents the use of this same problem set to perform spent fuel criticality benchmark calculations by replacing the actual fresh fuel isotopics from the experiments with six different sets of calculated spent fuel isotopics. The SCALE-4 modules SAS2H and CSAS4 were used to perform the analyses. These calculations do not model actual critical experiments. The calculated k-effectives are not supposed to equal unity and will vary depending on the initial enrichment and burnup of the calculated spent fuel isotopics. 12 refs., 11 tabs

Use of Multiple Linear Regression Method for Modelling Seasonal Changes in Stable Isotopes of 18O and 2H in 30 Pouns in Gilan Province

Directory of Open Access Journals (Sweden)

M.A. Mousavi Shalmani

2014-08-01

Full Text Available In order to assessment of water quality and characterize seasonal variation in 18O and 2H in relation with different chemical and physiographical parameters and modelling of effective parameters, an study was conducted during 2010 to 2011 in 30 different ponds in the north of Iran. Samples were collected at three different seasons and analysed for chemical and isotopic components. Data shows that highest amounts of δ18O and δ2H were recorded in the summer (-1.15‰ and -12.11‰ and the lowest amounts were seen in the winter (-7.50‰ and -47.32‰ respectively. Data also reveals that there is significant increase in d-excess during spring and summer in ponds 20, 21, 22, 24, 25 and 26. We can conclude that residual surface runoff (from upper lands is an important source of water to transfer soluble salts in to these ponds. In this respect, high retention time may be the main reason for movements of light isotopes in to the ponds. This has led d-excess of pond 12 even greater in summer than winter. This could be an acceptable reason for ponds 25 and 26 (Siyahkal county with highest amount of d-excess and lowest amounts of δ18O and δ2H. It seems light water pumped from groundwater wells with minor source of salt (originated from sea deep percolation in to the ponds, could may be another reason for significant decrease in the heavy isotopes of water (18O and 2H for ponds 2, 12, 14 and 25 from spring to summer. Overall conclusion of multiple linear regression test indicate that firstly from 30 variables (under investigation only a few cases can be used for identifying of changes in 18O and 2H by applications. Secondly, among the variables (studied, phytoplankton content was a common factor for interpretation of 18O and 2H during spring and summer, and also total period (during a year. Thirdly, the use of water in the spring was recommended for sampling, for 18O and 2H interpretation compared with other seasons. This is because of function can be

An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Viskolcz, Bé la; Farooq, Aamir

2015-01-01

We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

KAUST Repository

Khaled, Fathi

2015-10-30

We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

Extending and Enhancing SAS (Static Analysis Suite)

CERN Document Server

Ho, David

2016-01-01

The Static Analysis Suite (SAS) is an open-source software package used to perform static analysis on C and C++ code, helping to ensure safety, readability and maintainability. In this Summer Student project, SAS was enhanced to improve ease of use and user customisation. A straightforward method of integrating static analysis into a project at compilation time was provided using the automated build tool CMake. The process of adding checkers to the suite was streamlined and simplied by developing an automatic code generator. To make SAS more suitable for continuous integration, a reporting mechanism summarising results was added. This suitability has been demonstrated by inclusion of SAS in the Future Circular Collider Software nightly build system. Scalability of the improved package was demonstrated by using the tool to analyse the ROOT code base.

The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

Science.gov (United States)

Uchikawa, Joji; Zeebe, Richard E.

2012-10-01

Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

Science.gov (United States)

Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

2009-11-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the delta values of these reference materials should bracket the isotopic range of samples with unknown delta values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for delta13C and delta15N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as

H-superconducting cyclotron for PET isotope production

International Nuclear Information System (INIS)

Smirnov, V.L.; Vorozhtsov, S.B.; Vincent, J.

2014-01-01

The scientific design of a 14-MeV H - compact superconducting cyclotron for producing of the 18 F and 13 N isotopes has been developed. Main requirements to the facility as a medical accelerator are met in the design. In particular, the main requirement for the cyclotron was the smallest possible size due to the superconducting magnet. The calculations show that the proposed cyclotron allows extracted beam intensity over 500 μA. To increase system reliability and production rates, an external H - ion source is applied. The choice of the cyclotron concept, design of the structure elements, calculation of the electromagnetic fields and beam dynamics from the ion source to the extraction system were performed.

Homework Solutions S.A.S.

OpenAIRE

Acero Mora, Mariluz; Hernández Laguna, Liliana

2012-01-01

Homework Solutions S.A.S, será una empresa de servicios dedicada a brindar asesorías de tareas y trabajos bilingües con soluciones al instante sin que los padres de familia tengan que pagar por meses o semestres. Está previsto que dicha empresa empiece operaciones en el mes de Enero de 2013. Homework Solutions S.A.S, trabajará a domicilio, en los colegios que requieran sus servicios y en su sede principal ubicada al norte de la ciudad de Bogotá.

Prediction, Detection, and Validation of Isotope Clusters in Mass Spectrometry Data

Directory of Open Access Journals (Sweden)

Hendrik Treutler

2016-10-01

Full Text Available Mass spectrometry is a key analytical platform for metabolomics. The precise quantification and identification of small molecules is a prerequisite for elucidating the metabolism and the detection, validation, and evaluation of isotope clusters in LC-MS data is important for this task. Here, we present an approach for the improved detection of isotope clusters using chemical prior knowledge and the validation of detected isotope clusters depending on the substance mass using database statistics. We find remarkable improvements regarding the number of detected isotope clusters and are able to predict the correct molecular formula in the top three ranks in 92 % of the cases. We make our methodology freely available as part of the Bioconductor packages xcms version 1.50.0 and CAMERA version 1.30.0.

Isotopic evidence for the infiltration of mantle and metamorphic CO2-H2O fluids from below in faulted rocks from the San Andreas Fault System

Energy Technology Data Exchange (ETDEWEB)

Pili, E.; Kennedy, B.M.; Conrad, M.E.; Gratier, J.-P.

2010-12-15

To characterize the origin of the fluids involved in the San Andreas Fault (SAF) system, we carried out an isotope study of exhumed faulted rocks from deformation zones, vein fillings and their hosts and the fluid inclusions associated with these materials. Samples were collected from segments along the SAF system selected to provide a depth profile from upper to lower crust. In all, 75 samples from various structures and lithologies from 13 localities were analyzed for noble gas, carbon, and oxygen isotope compositions. Fluid inclusions exhibit helium isotope ratios ({sup 3}He/{sup 4}He) of 0.1-2.5 times the ratio in air, indicating that past fluids percolating through the SAF system contained mantle helium contributions of at least 35%, similar to what has been measured in present-day ground waters associated with the fault (Kennedy et al., 1997). Calcite is the predominant vein mineral and is a common accessory mineral in deformation zones. A systematic variation of C- and O-isotope compositions of carbonates from veins, deformation zones and their hosts suggests percolation by external fluids of similar compositions and origin with the amount of fluid infiltration increasing from host rocks to vein to deformation zones. The isotopic trend observed for carbonates in veins and deformation zones follows that shown by carbonates in host limestones, marbles, and other host rocks, increasing with increasing contribution of deep metamorphic crustal volatiles. At each crustal level, the composition of the infiltrating fluids is thus buffered by deeper metamorphic sources. A negative correlation between calcite {delta}{sup 13}C and fluid inclusion {sup 3}He/{sup 4}He is consistent with a mantle origin for a fraction of the infiltrating CO{sub 2}. Noble gas and stable isotope systematics show consistent evidence for the involvement of mantle-derived fluids combined with infiltration of deep metamorphic H{sub 2}O and CO{sub 2} in faulting, supporting the involvement of

Saturation and isotopic replacement of deuterium in low-Z material

International Nuclear Information System (INIS)

Doyle, B.L.; Wampler, W.R.; Brice, D.K.; Picraux, S.T.

1980-01-01

The saturation and replacement of hydrogen isotopes implanted into TiC, TiB 2 , VB 2 , B 4 C, B, Si, and C has been examined experimentally and modeled theoretically. The deuterium saturation concentrations for these materials varied from .16 to .57. A new isotopic replacement model is presented which predicts isotopic trapping and exchange on the basis of the depth dependence of the implanted ions and the experimentally determined hydrogen saturation concentration. Our results indicate that, for these materials used as coatings on components in a D-T fueled tokamak, T recovery by ion induced replacement with H or D should be feasible and that T buildup will be at tolerable levels

Limits on the expression of enzyme-mediated solvent isotope effects

International Nuclear Information System (INIS)

Northrop, D.B.

1981-01-01

Steady-state analysis of primary solvent isotope effects on enzyme-catalyzed reactions, mediated by solvent-shielded di- or triprotic groups on the enzyme, yields equations describing the upper limit of intramolecular isotopic discrimation. For diprotic groups [P/sub H]/[P/sub D/] = 3k/sub H//k/sub D/ + 3), and for triprotic groups [P/sub H/]/[P/sub D/] = [7(k/sub H//k/sub D/ 2 = 10k/sub H/k/sub D/ + 1]/[(k/sub H//k/sub D/) 2 + 10k/sub H//k/sub D/ + 7]. Given a normal intrinsic isotope effect of k/sub H//k/sub D/ = 7, maximal isotopic discrimation in 50:50 H 2 O:D 2 O is therefore 2.2 and 3.3, respectively, versus 1.0 for a monoprotic group. Intermediate values of isotope discrimination may be interpreted with respect to distinguishing enzyme-mediated catalytic mechanisms from those of direct transfer between solvent and substrate, and to identifying mediating groups, by comparisons of isotopic discrimination at high and low concentrations of substrates and by reference to intrinsic and intermolecular isotope effects

Laser ablation molecular isotopic spectrometry of water for {sub 1}D{sup 2}/{sub 1}H{sup 1} ratio analysis

Energy Technology Data Exchange (ETDEWEB)

Sarkar, Arnab [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Mao, Xianglei; Chan, George C.-Y. [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Russo, Richard E., E-mail: rerusso@lbl.gov [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States)

2013-10-01

Laser Ablation Molecular Isotopic Spectrometry (LAMIS) has been investigated for optical isotopic analysis of the deuterium to protium ratio in enriched water samples in ambient air at atmospheric pressure. Multivariate PLSR (Partial Least Squares Regression) based calibrations were carried out and validated using multiple statistical parameters. Comparisons of results are reported using two spectrometers having two orders of magnitude difference in spectral resolution. The accuracy and precision of isotopic analysis depends on the spectral resolution and the inherent isotope shift of the elements. The requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric processing of the spectra. Large isotopic shifts in the individual rotational branches of OH/OD molecular emission spectra were measured. Optimized temporal conditions for LAMIS measurements were established. Several sub-regions of spectra were used for PLSR calibration and the results demonstrate that both the emission intensity and degree of spectral differentiation affect the quality of the PLSR calibration. LAMIS results also were compared with traditional LIBS results obtained using PLSR and a spectral deconvolution method, demonstrating the advantages of LAMIS over LIBS with respect to isotopic composition determination. - Highlights: • D/H isotopic ratio in water over a large dynamic range was measured by LAMIS. • PLSR based multivariate calibration was used for construction of calibrations. • Region of interest significantly affects the analytical results of isotopic ratio. • LAMIS has improved results over LIBS irrespective of the spectrometer resolution. • The superiority is more prominent in the case using low resolution spectrometer.

Isotope exchange reaction in Li2ZrO3 packed bed

International Nuclear Information System (INIS)

Kawamura, Y.; Enoeda, M.; Okuno, K.

1998-01-01

To understand the release behavior of bred tritium in a solid breeder blanket, the tritium transfer rate and tritium inventory for various mass transfer processes should be investigated. The contribution of the surface reactions (adsorption, desorption and two kinds of isotope exchange reactions) to the release process cannot be ignored. It is believed that two kinds of isotope exchange reactions (gaseous hydrogen-tritiated water and water vapor-tritiated water) occur on the surface of the solid breeder materials when hydrogen is added to the sweep gas to enhance the tritium release rate. The isotope exchange reaction study in H-D systems was carried out using a Li 2 ZrO 3 packed bed. The exchange reaction between gaseous hydrogen and water was the rate controlling step among the two kinds of exchange reactions. The reaction rate constants were quantified, and experimental equations were proposed. The equilibrium constant of the isotope exchange reaction in the H-D system was obtained from experimental data and was found to be 1.17. (orig.)

ARP: A PC-compatible scheme for generating ORIGEN-S cross section library

International Nuclear Information System (INIS)

Leal, L.C.; Hermann, O.W.; Parks, C.V.

1995-01-01

The SAS2H sequence of the SCALE code system has been widely used for treating problems related to the characterization of nuclear systems for disposal, storage, and shipment. The calculations, in general, consist of determining the isotope compositions of the different materials present in the problem as a function of time, which subsequently enable determination of the heat generation and radiation source terms. In the SAS2H scheme, time-dependent material concentrations are obtained using the ORIGEN-S code based on a point-depletion calculation that utilizes problem-dependent cross-section libraries generated by distinct codes of the SAS2H sequence. In this paper we will be concerned with the methodology utilized in the SAS2H control module to create cross-section libraries for point-depletion calculations with the ORIGEN-S code. A brief description of the SAS2H scheme will be given, and a new capability, the automatic rapid processing (ARP), for generating problem-dependent ORIGEN-S cross-section libraries will be presented. Use of ARP can enable execution of ORIGEN-S on a personal computer with identical accuracy to that obtained with SAS2H

Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

Science.gov (United States)

Domagal-Goldman, S.; Kubicki, J. D.

2006-05-01

Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

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

Energy Technology Data Exchange (ETDEWEB)

Ward, Donald K. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Zhou, Xiaowang [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Karnesky, Richard A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Kolasinski, Robert [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Thurmer, Konrad [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Chao, Paul [Carnegie Mellon University, Pittsburgh, PA (United States); Epperly, Ethan Nicholas [Livermore Valley Charter Preparatory High School, Livermore, CA (United States); Zimmerman, Jonathan A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Wong, Bryan M. [Univ. of California, Riverside, CA (United States); Sills, Ryan B. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

2015-09-01

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

Comparison of force fields and calculation methods for vibration intervals of isotopic H+3 molecules

International Nuclear Information System (INIS)

Carney, G.D.; Adler-Golden, S.M.; Lesseski, D.C.

1986-01-01

This paper reports (a) improved values for low-lying vibration intervals of H + 3 , H 2 D + , D 2 H + , and D + 3 calculated using the variational method and Simons--Parr--Finlan representations of the Carney--Porter and Dykstra--Swope ab initio H + 3 potential energy surfaces, (b) quartic normal coordinate force fields for isotopic H + 3 molecules, (c) comparisons of variational and second-order perturbation theory, and (d) convergence properties of the Lai--Hagstrom internal coordinate vibrational Hamiltonian. Standard deviations between experimental and ab initio fundamental vibration intervals of H + 3 , H 2 D + , D 2 H + , and D + 3 for these potential surfaces are 6.9 (Carney--Porter) and 1.2 cm -1 (Dykstra--Swope). The standard deviations between perturbation theory and exact variational fundamentals are 5 and 10 cm -1 for the respective surfaces. The internal coordinate Hamiltonian is found to be less efficient than the previously employed ''t'' coordinate Hamiltonian for these molecules, except in the case of H 2 D +

Measurement of the D/H, 18O/16O, and 17O/16O Isotope Ratios in Water by Laser Absorption Spectroscopy at 2.73 μm

Directory of Open Access Journals (Sweden)

Tao Wu

2014-05-01

Full Text Available A compact isotope ratio laser spectrometry (IRLS instrument was developed for simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in water by laser absorption spectroscopy at 2.73 μm. Special attention is paid to the spectral data processing and implementation of a Kalman adaptive filtering to improve the measurement precision. Reduction of up to 3-fold in standard deviation in isotope ratio determination was obtained by the use of a Fourier filtering to remove undulation structure from spectrum baseline. Application of Kalman filtering enables isotope ratio measurement at 1 s time intervals with a precision (<1‰ better than that obtained by conventional 30 s averaging, while maintaining a fast system response. The implementation of the filter is described in detail and its effects on the accuracy and the precision of the isotope ratio measurements are investigated.

Isotopic equilibrium constants of the deuterium exchange between HDO and H{sub 2}S, H{sub 2}Se and H{sub 2}Te; Etude des constantes des equilibres isotopiques du deuterium entre l'eau et les hydrures des metalloides de la deuxieme famille

Energy Technology Data Exchange (ETDEWEB)

Marx, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1959-11-15

We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. In gaseous phase, statistical thermodynamics leads to the expression: K (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [French] Nous avons determine experimentalement la constante K de chacun des equilibres isotopiques suivants: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. En phase gazeuse, la thermodynamique donne l'expression: K = (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R representant un atome de soufre, selenium ou tellure). Les fonctions de partition Z de chacune des molecules ont ete calculees et, grace a nos resultats experimentaux, nous avons determine la constante W. Connaissant W, la constante d'equilibre K a pu etre tabulee en fonction de la temperature. (auteur)

A demonstration of the 'isotope wind tunnel principle' in JET and its use in predicting reactor performance

International Nuclear Information System (INIS)

Cordey, J.; Alper, B.; Budny, R.

2000-01-01

ELMy H-mode pulses have been obtained with different hydrogenic isotopes (H and D) but having the same profiles of the dimensionless parameters ρ*, β*, ν* and q, to test whether the confinement scale invariance principle is valid in a tokamak. The fact that the confinement times, the ELM and sawtooth frequencies in the two pulses all scale as expected suggests that the invariance principle is satisfied through the plasma radial extent, in spite of the differing physical processes taking place in the plasma centre, core and edge regions. An application of this 'isotope windtunnel technique' to predicting D-T performance of next step devices is discussed. In tokamak discharges, such as the steady state ELMy H-mode, the physical processes change dramatically as one moves out in minor radius. In the central region the temperature gradient is controlled by MHD modes (sawteeth), whilst outside in what is known as the core confinement region the transport is thought to be due to small scale Larmor radius (r i ) size turbulence, such as that caused by the ion temperature gradient instability. Finally in the edge region the transport is almost neoclassical with intermittent MHD events (ELMs) controlling the steepness of the gradients in this region. From theoretical analysis, in particular the confinement scale invariance principle, it should be possible to describe the transport properties in all three regions in terms of the profiles of the basic dimensionless plasma physics parameters ρ*(∝(MT) 1/2 /aB), β(∝ nT/B 2 ), ν* (∝ na/T 2 ) and q (∝Bκ/Rj). The thermal diffusivity should have the form χ ∝ Ba 2 /M F(ρ*, β, ν*, q, ...) where the form of the function F will be different in each of the three regions. One method of checking whether the invariance principle is correct is to complete wind tunnel or identity experiments on different tokamaks. This involves setting up discharges on different tokamaks with the same profiles of ρ*, β, ν* and q and

Relative mobility of 1-H atoms of carbohydrates in heterogeneous isotope exchange reactions

International Nuclear Information System (INIS)

Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskii, Yu.L.

1988-01-01

The method of competitive reactions was used to determine the relative mobilities of the 1-H atoms of carbohydrates in reactions of heterogeneous isotope exchange, using various reference standards, catalysts, and buffer systems. On the basis of the results obtained, the investigated carbohydrates are ranged in a series of decreasing mobility of the hydrogen atoms exchanged in heterogeneous isotope exchange reactions. It was demonstrated that the mobility of the 1-H atoms is related to the concentration of the acyclic forms of the carbohydrates

Utilization of stable isotopes for characterizing an underground gas generator; Utilisation des isotopes stables pour caracteriser un gazogene souterrain

Energy Technology Data Exchange (ETDEWEB)

Pirard, J P; Antenucci, D; Renard, X [Liege Univ. (Belgium); Letolle, R [Paris-6 Univ., 75 (France)

1994-12-31

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O{sub 2}, H{sub 2}O) and in the effluent (CO{sub 2}, CO, H{sub 2}, H{sub 2}O, CH{sub 4}, O{sub 2}, heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs.

Isotope effects accompanying evaporation of water from leaky containers.

Science.gov (United States)

Rozanski, Kazimierz; Chmura, Lukasz

2008-03-01

Laboratory experiments aimed at quantifying isotope effects associated with partial evaporation of water from leaky containers have been performed under three different settings: (i) evaporation into dry atmosphere, performed in a dynamic mode, (ii) evaporation into dry atmosphere, performed in a static mode, and (iii) evaporation into free laboratory atmosphere. The results demonstrate that evaporative enrichment of water stored in leaky containers can be properly described in the framework of the Craig-Gordon evaporation model. The key parameter controlling the degree of isotope enrichment is the remaining fraction of water in the leaking containers. Other factors such as temperature, relative humidity, or extent of kinetic fractionation play only minor roles. Satisfactory agreement between observed and predicted isotope enrichments for both (18)O and (2)H in experiments for the case of evaporation into dry atmosphere could be obtained only when molecular diffusivity ratios of isotope water molecules as suggested recently by Cappa et al. [J. Geophys. Res., 108, 4525-4535, (2003).] were adopted. However, the observed and modelled isotope enrichments for (2)H and (18)O could be reconciled also for the ratios of molecular diffusivities obtained by Merlivat [J. Chem. Phys., 69, 2864-2871 (1978).], if non-negligible transport resistance in the viscous liquid sub-layer adjacent to the evaporating surface is considered. The evaporation experiments revealed that the loss of mass of water stored in leaky containers in the order of 1%, will lead to an increase of the heavy isotope content in this water by ca. 0.35 and 1.1 per thousand, for delta (18)O and delta (2)H, respectively.

Laser spectrometry applied to the simultaneous determination of the δ2H, δ17O, and δ18O isotope abundances in water

International Nuclear Information System (INIS)

Kerstel, E.R.T.; Trigt, R. van; Dam, N.; Reuss, J.; Meijer, H.A.J.

2001-01-01

We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative 2 H/ 1 H, 17 O/ 16 O, and 18 O/ 16 O isotope abundance ratios in natural water. The method uses a narrow line width color center laser to record the direct absorption spectrum of low-pressure gas-phase water samples (presently 10 μl liquid) in the 3μm spectral region. The precision of the spectroscopic technique is shown to be 0.7 per mille for δ 2 H and 0.5 per mille for δ 17 O and δ 18 O, while the calibrated accuracy for natural waters amounts to about 3 per mille and 1 per mille, respectively. (author)

Predicting rates of isotopic turnover across the animal kingdom: a synthesis of existing data.

Science.gov (United States)

Thomas, Stephen M; Crowther, Thomas W

2015-05-01

The stable isotopes of carbon ((12)C, (13)C) and nitrogen ((14)N, (15)N) represent powerful tools in food web ecology, providing a wide range of dietary information in animal consumers. However, identifying the temporal window over which a consumer's isotopic signature reflects its diet requires an understanding of elemental incorporation, a process that varies from days to years across species and tissue types. Though theory predicts body size and temperature are likely to control incorporation rates, this has not been tested empirically across a morphologically and phylogenetically diverse range of taxa. Readily available estimates of this relationship would, however, aid in the design of stable isotope food web investigations and improve the interpretation of isotopic data collected from natural systems. Using literature-derived turnover estimates from animal species ranging in size from 1 mg to 2000 kg, we develop a predictive tool for stable isotope ecologists, allowing for estimation of incorporation rates in the structural tissues of entirely novel taxa. In keeping with metabolic scaling theory, we show that isotopic turnover rates of carbon and nitrogen in whole organisms and muscle tissue scale allometrically with body mass raised approximately to the power -0.19, an effect modulated by body temperature. This relationship did not, however, apply to incorporation rates in splanchnic tissues, which were instead dependent on the thermoregulation tactic employed by an organism, being considerably faster in endotherms than ectotherms. We believe the predictive turnover equations we provide can improve the design of experiments and interpretation of results obtained in future stable isotopic food web studies. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.

The synthesis of 7-chloro-5-pentadeuteriophenyl-1-methyl-1H-1, 5-benzodiazepine-2,4(3H, 5H)dione (( sup 2 H sub 5 )clobazam)

Energy Technology Data Exchange (ETDEWEB)

Borel, A.G.; Abbott, F.S. (British Columbia Univ., Vancouver, BC (Canada). Dept. of Pharmaceutical Sciences)

1990-07-01

Pentadeuteriophenyl clobazam was synthesized in essentially quantitative isotopic purity, and characterized by {sup 1}H-NMR and mass spectroscopy. The title compound was found to be >98% pure by HPLC, and its retention time (t{sub R} 6.17 min) was less than that of an authentic clobazam standard (t{sub R} 6.32 min). Of the five steps in the synthesis of clobazam, the most susceptible to deuterium exchange was the nucleophilic substitution of 2,4-dichloronitrobenzene by aniline-d{sub 7} to form N-(5-chloro-2-nitrophenyl)penta-deuteriophenylamine. In this step, the isotopic impurity aniline-2,3,4,5-d{sub 5} introduced protons from nitrogen into the ortho and para positions of the deuteriophenyl ring of N-(5-chloro-2-nitrophenyl)pentadeuteriophenylamine. (author).

H, C, N and S stable isotopes and mineral profiles to objectively guarantee the authenticity of grated hard cheeses

International Nuclear Information System (INIS)

Camin, Federica; Wehrens, Ron; Bertoldi, Daniela; Bontempo, Luana; Ziller, Luca; Perini, Matteo; Nicolini, Giorgio; Nocetti, Marco; Larcher, Roberto

2012-01-01

Graphical abstract: Random Forest model based on δ 13 C, δ 2 H, δ 15 N, δ 34 S and the content of Sr, Cu, Mo, Re, Na, U, Bi, Ni, Fe, Mn, Ga, Se, Er, Dy, Pb, Li, usable for the protection of PDO Parmigiano Reggiano cheese from mislabelling. The correct classification rate in cross-validation is 98.6%. Highlights: ► The isotopic and elemental profile of over 260 hard cheese samples are discussed. ► Two validated and immediately applicable statistical models are presented. ► One model is able to predict the origin of seven types of European hard cheeses. ► The other one allows to discriminate the PDO Parmigiano Reggiano cheese from imitators. ► The most significant variables are δ 13 C, δ 2 H, δ 15 N, δ 34 S and the content of 16 elements. - Abstract: In compliance with the European law (EC No. 510/2006), geographical indications and designations of origin for agricultural products and foodstuffs must be protected against mislabelling. This is particularly important for PDO hard cheeses, as Parmigiano Reggiano, that can cost up to the double of the no-PDO competitors. This paper presents two statistical models, based on isotopic and elemental composition, able to trace the origin of cheese also in grated and shredded forms, for which it is not possible to check the logo fire-marked on the rind. One model is able to predict the origin of seven types of European hard cheeses (in a validation step, 236 samples out of 240 are correctly recognised) and the other specifically to discriminate the PDO Parmigiano Reggiano cheese from 9 European and 2 extra-European imitators (260 out of 264 correct classifications). Both models are based on Random Forests. The most significant variables for cheese traceability common in both models are δ 13 C, δ 2 H, δ 15 N, δ 34 S and Sr, Cu, Mo, Re, Na, U, Bi, Ni, Fe, Mn, Ga, Se, and Li. These variables are linked not only to geography, but also to cow diet and cheese making processes.

Deuterium isotope effects on 13C chemical shifts of 10-Hydroxybenzo[h]quinolines

DEFF Research Database (Denmark)

Hansen, Poul Erik; Kamounah, Fadhil S.; Gryko, Daniel T.

2013-01-01

Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...

A numerical model for the movement of H 2O, H 218O, and 2HHO in the unsaturated zone

Science.gov (United States)

Shurbaji, Abdel-Rahman M.; Phillips, Fred M.

1995-09-01

Vertical profiles of H 218O and 2HHO concentrations have yielded useful information on evaporation and infiltration processes in soils. However, in the field, quantitative interpretation of such profiles has been limited by the restrictions inherent in the quasi-steady-state and transient analytical models available to describe the physical processes. This study presents a flexible numerical model that simulates transient fluxes of heat, liquid water, water vapor, and isotopic species. The model can simulate both infiltration and evaporation under fluctuating meteorological conditions and thus should be useful in reproducing changes in field isotope profiles. A transition factor is introduced in the isotope transport equation. This factor combines hydrologic and isotopic parameters and changes slowly with depth in the soil profile but strongly in the evaporation zone, owing to the rapid change in the dominant phase of water from liquid to vapor. Using the transition factor in the isotope transport equation facilitates obtaining the typical shape of the isotope profile (bulge at the evaporation zone). This factor also facilitates producing broad isotope enrichment peaks that may be seen in very dry soils.

Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

Science.gov (United States)

Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.;

Kinetics of isotopic exchange of [1-3H]saccharides with hydrogen using palladium catalysts

International Nuclear Information System (INIS)

Akulov, G.P.; Kayumov, V.G.; Snetkova, E.V.; Kaminskij, Yu.L.

1988-01-01

The kinetics was studied of the isotopic exchange of [1- 3 H]saccharides with hydrogen on palladium catalysts. The effect was studied of different factors on the rate of isotopic exchange, e.g., of the composition and structure of saccharides, their concentration in the solution (C), the type of catalyst and of the buffer solution. It was found that by reduced rate of isotopic exchange with hydrogen, all studied saccharides may be arranged into a series independent of the type of catalyst in accordance with the sequence of declining coefficient of relative mobility of l-H atoms during the reaction. Linear dependence was found to exist between the rate constant of the isotopic exchange reaction (r) and the coefficient of relative lability. It was also found that in the range of low concentrations the observed rate constants of isotopic exchange were not dependent on concentration and in the range of higher concentrations, r decreased with increasing C. This character of dependence is justified by the side effect of the processes of sorption on the catalyst. (author). 3 figs., 1 tab., 4 refs

Particle and particle systems characterization small-angle scattering (SAS) applications

CERN Document Server

Gille, Wilfried

2016-01-01

Small-angle scattering (SAS) is the premier technique for the characterization of disordered nanoscale particle ensembles. SAS is produced by the particle as a whole and does not depend in any way on the internal crystal structure of the particle. Since the first applications of X-ray scattering in the 1930s, SAS has developed into a standard method in the field of materials science. SAS is a non-destructive method and can be directly applied for solid and liquid samples. Particle and Particle Systems Characterization: Small-Angle Scattering (SAS) Applications is geared to any scientist who might want to apply SAS to study tightly packed particle ensembles using elements of stochastic geometry. After completing the book, the reader should be able to demonstrate detailed knowledge of the application of SAS for the characterization of physical and chemical materials.

2H Kinetic Isotope Effects and pH Dependence of Catalysis as Mechanistic Probes of Rat Monoamine Oxidase A: Comparisons with the Human Enzyme‡

Science.gov (United States)

Wang, Jin; Edmondson, Dale E.

2011-01-01

Monoamine oxidase A (MAO A) is a mitochondrial outer membrane-bound flavoenzyme important in the regulation of serotonin and dopamine levels. Since the rat is extensively used as an animal model in drug studies, it is important to understand how rat MAO A behaves in comparison with the more extensively studied human enzyme. For many reversible inhibitors, rat MAO A exhibits Ki values similar to those of human MAO A. The pH profile of kcat for rat MAO A shows a pKa of 8.2±0.1 for the benzylamine ES complex and pKa values of 7.5±0.1 and 7.6±0.1 for the respective ES complexes with p-CF3-1H and p-CF3-2H-benzylamine. In contrast to the human enzyme, the rat enzyme exhibits a single pKa value (8.3±0.1) with kcat/Km benzylamine vs. pH and pKa values of 7.8±0.1 and 8.1±0.2 are found for the ascending limbs, respectively, of kcat/Km vs. pH profiles for p-CF3-1H and p-CF3-2H-benzylamine and 9.3±0.1 and 9.1±0.2 for their respective descending limbs. The oxidation of para-substituted benzylamine substrate analogues by rat MAO A exhibit large deuterium kinetic isotope effects on kcat and on kcat/Km. These effects are pH-independent, and range from 7 to 14, demonstrating a rate-limiting α-C-H bond cleavage step in catalysis. Quantitative structure-activity correlations of log kcat with the electronic substituent parameter (σ) at pH 7.5 and at 9.0 show a dominant contribution with positive ρ values (+1.2 – 1.3) and a pH-independent negative contribution from the steric term. Quantitative structure-activity relationship analysis of the binding affinities of the para-substituted benzylamine analogues to rat MAO A show an increased van der Waals volumes (Vw) increases the affinity of the deprotonated amine for the enzyme. These results demonstrate that rat MAO A exhibits similar but not identical functional properties with the human enzyme and provide additional support for C-H bond cleavage via a polar nucleophilic mechanism. PMID:21819071

Positional enrichment by proton analysis (PEPA). A one-dimensional "1H-NMR approach for "1"3C stable isotope tracer studies in metabolomics

International Nuclear Information System (INIS)

Vinaixa, Maria; Yanes, Oscar; Rodriguez, Miguel A.; Capellades, Jordi; Aivio, Suvi; Stracker, Travis H.; Gomez, Josep; Canyellas, Nicolau

2017-01-01

A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of "1"3C-satellite peaks using 1D-"1H-NMR spectra. In comparison with "1"3C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of "1"3C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of "1H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

Does age matter? Controls on the spatial organization of age and life expectancy in hillslopes, and implications for transport parameterization using rSAS

Science.gov (United States)

Kim, M.; Harman, C. J.; Troch, P. A. A.

2017-12-01

Hillslopes have been extensively explored as a natural fundamental unit for spatially-integrated hydrologic models. Much of this attention has focused on their use in predicting the quantity of discharge, but hillslope-based models can potentially be used to predict the composition of discharge (in terms of age and chemistry) if they can be parameterized terms of measurable physical properties. Here we present advances in the use of rank StorAge Selection (rSAS) functions to parameterize transport through hillslopes. These functions provide a mapping between the distribution of water ages in storage and in outfluxes in terms of a probability distribution over storage. It has previously been shown that rSAS functions are related to the relative partitioning and arrangement of flow pathways (and variabilities in that arrangement), while separating out the effect of changes in the overall rate of fluxes in and out. This suggests that rSAS functions should have a connection to the internal organization of flow paths in a hillslope.Using a combination of numerical modeling and theoretical analysis we examined: first, the controls of physical properties on internal spatial organization of age (time since entry), life expectancy (time to exit), and the emergent transit time distribution and rSAS functions; second, the possible parameterization of the rSAS function using the physical properties. The numerical modeling results showed the clear dependence of the rSAS function forms on the physical properties and relations between the internal organization and the rSAS functions. For the different rates of the exponential saturated hydraulic conductivity decline with depth the spatial organization of life expectancy varied dramatically and determined the rSAS function forms, while the organizaiton of the age showed less qualitative differences. Analytical solutions predicting this spatial organization and the resulting rSAS function were derived for simplified systems. These

Aging of nickel added to soils as predicted by soil pH and time.

Science.gov (United States)

Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J; Oliver, Ian W; Nolan, Annette L; Oorts, Koen; Smolders, Erik

2013-08-01

Although aging processes are important in risk assessment for metals in soils, the aging of Ni added to soils has not been studied in detail. In this study, after addition of water soluble Ni to soils, the changes over time in isotopic exchangeability, total concentrations and free Ni(2+) activity in soil pore water, were investigated in 16 European soils incubated outdoors for 18 months. The results showed that after Ni addition, concentrations of Ni in soil pore water and isotopic exchangeability of Ni in soils initially decreased rapidly. This phase was followed by further decreases in the parameters measured but these occurred at slower rates. Increasing soil pH increased the rate and extent of aging reactions. Semi-mechanistic models, based on Ni precipitation/nucleation on soil surfaces and micropore diffusion, were developed and calibrated. The initial fast processes, which were attributed to precipitation/nucleation, occurred over a short time (e.g. 1h), afterwards the slow processes were most likely controlled by micropore diffusion processes. The models were validated by comparing predicted and measured Ni aging in three additional, widely differing soils aged outdoors for periods up to 15 months in different conditions. These models could be used to scale ecotoxicological data generated in short-term studies to longer aging times. Copyright © 2013 Elsevier Ltd. All rights reserved.

Observation of Isotope Ratios (δ2H, δ18O, 87Sr/86Sr) of Tap Water in Urban Environments

Science.gov (United States)

Mancuso, C. J.; Tipple, B. J.; Ehleringer, J. R.

2014-12-01

Urban environments are centers for rapidly growing populations. In order to meet the culinary water needs of these areas, municipal water departments use water from multiple locations and/or sources, often piped differentially to different locations within a municipality. This practice creates isotopically distinct locations within an urban area and therefore provides insight to urban water management practices. In our study we selected urban locations in the Salt Lake Valley, UT (SLV) and San Francisco Bay Area, CA (SFB) where we hypothesized geographically distinct water isotopic ratio differences existed. Within the SLV, municipal waters come from the same mountainous region, but are derived from different geologically distinct watersheds. In contrast, SFB waters are derived from regionally distinct water sources. We hypothesized that the isotope ratios of tap waters would differ based upon known municipal sources. To test this, tap water samples were collected throughout the urban regions in SLV and SFB and analyzed for δ2H, δ18O and 87Sr/86Sr isotope ratios. Seasonal collections were also made to assess if isotope ratios differed throughout the year. Within SLV and SFB, different regions were characterized by distinct paired δ18O and 87Sr/86Sr values. These different realms also agreed with known differences in municipal water supplies within the general geographic region. Waters from different cities within Marin County showed isotopic differences, consistent with water derived from different local reservoirs. Seasonal variation was observed in paired δ18O and 87Sr/86Sr values of tap water for some locations within SLV and SFB, indicating management decisions to shift from one water source to another depending on demand and available resources. Our study revealed that the δ18O and 87Sr/86Sr values of tap waters in an urban region can exhibit significant differences despite close spatial proximity if districts differ in their use of local versus

A SAS IML Macro for Loglinear Smoothing

Science.gov (United States)

Moses, Tim; von Davier, Alina

2011-01-01

Polynomial loglinear models for one-, two-, and higher-way contingency tables have important applications to measurement and assessment. They are essentially regarded as a smoothing technique, which is commonly referred to as loglinear smoothing. A SAS IML (SAS Institute, 2002a) macro was created to implement loglinear smoothing according to…

Melnās krāsas iespējas interjerā

OpenAIRE

Lapkovska, Ērika

2016-01-01

Diplomdarbā “Melnās krāsas iespējas interjerā”, analizējot pieejamo literatūru, tiek apskatīta melnās krāsas izpratne, nozīme un lietojums vēsturiskā skatījumā, kā arī melnās krāsas izmantojuma principi interjerā. Empīriskajā daļā tiek veikts salīdzinošais pētījums, analizējot dažādus kafejnīcu un bāru interjerus Latvijā un pasaulē, kuros ir melnās krāsas klātbūtne. Diplomdarba apjoms – 75 lpp., kurās iekļauts ievads, 4 nodaļas, 7 apakšnodaļas, literatūras saraksts ar 53 vienībām, 2 pielikum...

Regression modeling methods, theory, and computation with SAS

CERN Document Server

Panik, Michael

2009-01-01

Regression Modeling: Methods, Theory, and Computation with SAS provides an introduction to a diverse assortment of regression techniques using SAS to solve a wide variety of regression problems. The author fully documents the SAS programs and thoroughly explains the output produced by the programs.The text presents the popular ordinary least squares (OLS) approach before introducing many alternative regression methods. It covers nonparametric regression, logistic regression (including Poisson regression), Bayesian regression, robust regression, fuzzy regression, random coefficients regression,

The Global Network of Isotopes in Precipitation after 55 years: assessing past, present and future developments

Science.gov (United States)

Terzer, Stefan; Araguas-Araguas, Luis; Wassenaar, Leonard I.; Aggarwal, Pradeep K.

2015-04-01

The Global Network of Isotopes in Precipitation (GNIP) is a global observation programme operated by the International Atomic Energy Agency (IAEA), in cooperation with the World Meteorological Organization (WMO) and more than 100 contributing institutions worldwide. GNIP has been the primary repository for baseline stable (δ18O, δ2H) and radioactive (3H) isotope data since its foundation in 1960. The impetus for GNIP was the monitoring of radioactive fallout from atmospheric thermonuclear testing and resulting tritium levels of precipitation, but tritium together with stable isotopes was recognized as a key to understanding hydrological processes. Later, new applications were developed focusing on hydrometeorology and paleoclimatic research. Increasingly, GNIP data are being used more widely in ecological and forensic investigations, e.g. for tracking of migratory animals. The GNIP database comprises more than 135,000 isotopic records (δ18O: 63,000; δ2H: 55,000; 3H: 63,000) of monthly composite precipitation samples from more than 1,000 stations worldwide. About 300 stations are currently active for stable isotopes and ca. 100 for tritium. Data for most of the active stations is available up to 2013. Several national isotopic observation networks (e.g. in Austria, Australia, China or the United States of America) exist besides GNIP, complementing precipitation isotope data at national levels. The spatially and temporally discrete nature of the GNIP dataset induces coverage gaps. Recently, highly-resolved gridded datasets were established to help overcome this deficiency through geostatistical prediction models. These 'isoscape' (isotopic landscapes) are based on combinations of multiple regression and interpolation methods, with a range of parameterization available at regional and global levels. Attempts to bridge the gap between 'one-size-fits-all' global parameterization and improved predictions at regional and local levels led to the establishment of a

Effects of hyperglycemia on glucose production and utilization in humans. Measurement with [3H]-2-, [3H]-3-, and [14C]-6-glucose

International Nuclear Information System (INIS)

Bell, P.M.; Firth, R.G.; Rizza, R.A.

1986-01-01

Studies with tritiated isotopes of glucose have demonstrated that hyperglycemia per se stimulates glucose utilization and suppresses glucose production in humans. These conclusions rely on the assumption that tritiated glucose provides an accurate measure of glucose turnover. However, if in the presence of hyperglycemia the isotope either loses its label during futile cycling or retains its label during cycling through glycogen, then this assumption is not valid. To examine this question, glucose utilization and glucose production rates were measured in nine normal subjects with a simultaneous infusion of [ 3 H]-2-glucose, an isotope that may undergo futile cycling but does not cycle through glycogen; [ 14 C]-6-glucose, an isotope that may cycle through glycogen but does not futile cycle; and [ 3 H]-3-glucose, an isotope that can both undergo futile cycling and cycle through glycogen. In the postabsorptive state at plasma glucose concentration of 95 mg X dl-1, glucose turnover determined with [ 14 C]-6-glucose (2.3 +/- 0.1 mg X kg-1 X min-1) was greater than that determined with [3 3 H]glucose (2.1 +/- 0.1 mg X kg-1 X min-1, P = 0.002) and slightly less than that determined with [ 3 H]-2-glucose (2.7 +/- 0.2 mg X kg-1 X min-1, P = 0.08). Plasma glucose was then raised from 95 to 135 to 175 mg X dl-1 while insulin secretion was inhibited, and circulating insulin, glucagon, and growth hormone concentrations were maintained constant by infusion of these hormones and somatostatin. Glucose production and utilization rates determined with [ 14 C]-6-glucose continued to be less than those determined with [ 3 H]-2-glucose and greater than those seen with [ 3 H]-3-glucose

Deuterium isotopic effects connected with unimolecular and concerted mechanisms. The case of 1-deutero-2-chloro alcohols

International Nuclear Information System (INIS)

Jambon, C.

1962-01-01

After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [fr

Effects of variation in background mixing ratios of N2, O2, and Ar on the measurement of δ18O-H2O and δ2H-H2O values by cavity ring-down spectroscopy

Science.gov (United States)

Johnson, Jennifer E.; Rella, Chris W.

2017-08-01

Cavity ring-down spectrometers have generally been designed to operate under conditions in which the background gas has a constant composition. However, there are a number of observational and experimental situations of interest in which the background gas has a variable composition. In this study, we examine the effect of background gas composition on a cavity ring-down spectrometer that measures δ18O-H2O and δ2H-H2O values based on the amplitude of water isotopologue absorption features around 7184 cm-1 (L2120-i, Picarro, Inc.). For background mixtures balanced with N2, the apparent δ18O values deviate from true values by -0.50 ± 0.001 ‰ O2 %-1 and -0.57 ± 0.001 ‰ Ar %-1, and apparent δ2H values deviate from true values by 0.26 ± 0.004 ‰ O2 %-1 and 0.42 ± 0.004 ‰ Ar %-1. The artifacts are the result of broadening, narrowing, and shifting of both the target absorption lines and strong neighboring lines. While the background-induced isotopic artifacts can largely be corrected with simple empirical or semi-mechanistic models, neither type of model is capable of completely correcting the isotopic artifacts to within the inherent instrument precision. The development of strategies for dynamically detecting and accommodating background variation in N2, O2, and/or Ar would facilitate the application of cavity ring-down spectrometers to a new class of observations and experiments.

[A SAS marco program for batch processing of univariate Cox regression analysis for great database].

Science.gov (United States)

Yang, Rendong; Xiong, Jie; Peng, Yangqin; Peng, Xiaoning; Zeng, Xiaomin

2015-02-01

To realize batch processing of univariate Cox regression analysis for great database by SAS marco program. We wrote a SAS macro program, which can filter, integrate, and export P values to Excel by SAS9.2. The program was used for screening survival correlated RNA molecules of ovarian cancer. A SAS marco program could finish the batch processing of univariate Cox regression analysis, the selection and export of the results. The SAS macro program has potential applications in reducing the workload of statistical analysis and providing a basis for batch processing of univariate Cox regression analysis.

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Science.gov (United States)

Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

2009-01-01

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back

Study of peculiarities of hydrogen isotopes mixture permeation through low activated steel F82H

International Nuclear Information System (INIS)

Kenzhin, Ye.A.; Tazhibayeva, I.L; Kulsartov, T.V.; Shestakov, V.P.; Chikhray, Ye.V.; Afanasev, S.E.; Zheldak, Yu.L.

2003-01-01

Full text: The problem of diffusion tritium leakage through blanket materials of future fusion device makes some constructive difficulties concerned with protection of personnel and environment and also with losses of tritium, which is planned to be used in the same device. One of the little-studied problems in the tritium leakage process in Fusion Power Plant is that in fact tritium will penetrate through materials while other hydrogen isotopes are present. These are deuterium and hydrogen which always are present in metals. Therefore, for evaluation of tritium leakage in future Fusion Power Plant under such conditions it is necessary to have experimental data about permeation of these hydrogen isotopes through the structure materials.One of proposed structure materials of fusion reactor blanket is low activated steel F82H. The experiment results on evaluation of .hydrogen, deuterium and its mixture interaction parameters with steel F82H are shown in this work. The tests were carried out within temperature range 273-973 K under inlet hydrogen pressure of 100-2000 Pa. Diffusivity, deuterium and hydrogen permeation constants for low activated steel F82H was determined from experiment results. Those experimental results were used for created phenomenology model which describes hydrogen isotope penetration through tube sample from hydrogen isotopes mixture. That model was used so determining the ratios of desorption rates (D-D, D-H, H-H) on outlet side of sample. Using of so obtained results, we can correctly evaluate, the titanium leakage from blanket of fusion machine which will be constructed using low activated steel F82H

A new package: MySAS for small angle scattering data analysis

International Nuclear Information System (INIS)

Huang Chaoqiang; Xia Qingzhong; Yan Guanyun; Sun Guang'ai; Chen Bo

2010-01-01

In this paper, A MySAS package, which is verified on Windows XP, can easily convert two-dimensional data in small angle neutron and X-ray scattering analysis, operate individually and execute one particular operation as numerical data reduction or analysis, and graphical visualization. This MySAS package can implement the input and output routines via scanning certain properties, thus recalling completely sets of repetition input and selecting the input files. On starting from the two-dimensional files, the MySAS package can correct the anisotropic or isotropic data for physical interpretation and select the relevant pixels. Over 50 model functions are fitted by the POWELL code using χ 2 as the figure of merit function. (authors)

Positional enrichment by proton analysis (PEPA). A one-dimensional {sup 1}H-NMR approach for {sup 13}C stable isotope tracer studies in metabolomics

Energy Technology Data Exchange (ETDEWEB)

Vinaixa, Maria; Yanes, Oscar [Department of Electronic Engineering-Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Rodriguez, Miguel A.; Capellades, Jordi [Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Aivio, Suvi; Stracker, Travis H. [Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (Spain); Gomez, Josep; Canyellas, Nicolau [Department of Electronic Engineering-, Universitat Rovira i Virgili, Tarragona (Spain)

2017-03-20

A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of {sup 13}C-satellite peaks using 1D-{sup 1}H-NMR spectra. In comparison with {sup 13}C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of {sup 13}C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of {sup 1}H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

pH-Free Measurement of Relative Acidities, Including Isotope Effects.

Science.gov (United States)

Perrin, Charles L

2017-01-01

A powerful pH-free multicomponent NMR titration method can measure relative acidities, even of closely related compounds, with excellent accuracy. The history of the method is presented, along with details of its implementation and a comparison with earlier NMR titrations using a pH electrode. Many of its areas of applicability are described, especially equilibrium isotope effects. The advantages of the method, some practical considerations, and potential pitfalls are considered. © 2017 Elsevier Inc. All rights reserved.

Tracing and quantifying lake water and groundwater fluxes in the area under mining dewatering pressure using coupled O and H stable isotope approach.

Science.gov (United States)

Lewicka-Szczebak, Dominika; Jędrysek, Mariusz-Orion

2013-01-01

Oxygen and hydrogen stable isotopic compositions of precipitation, lake water and groundwater were used to quantitatively asses the water budget related to water inflow and water loss in natural lakes, and mixing between lake water and aquifer groundwater in a mining area of the Lignite Mine Konin, central Poland. While the isotopic composition of precipitation showed large seasonal variations (δ(2)H from-140 to+13 ‰ and δ(18)O from-19.3 to+7.6 ‰), the lake waters were variously affected by evaporation (δ(2)H from-44 to-21 ‰ and δ(18)O from-5.2 to-1.7 ‰) and the groundwater showed varying contribution from mixing with surface water (δ(2)H from-75 to-39 ‰ and δ(18)O from-10.4 to-4.8 ‰). The lake water budget was estimated using a Craig-Gordon model and isotopic mass balance constraint, which enabled us to identify various water sources and to quantify inflow and outflow for each lake. Moreover, we documented that a variable recharge of lake water into the Tertiary aquifer was dependent on mining drainage intensity. A comparison of coupled δ(2)H-δ(18)O data with hydrogeological results indicated better precision of the δ(2)H-based calculations.

Genesis of fumarolic emissions as inferred by isotope mass balances: CO 2 and water at Vulcano Island, Italy

Science.gov (United States)

Paonita, A.; Favara, R.; Nuccio, P. M.; Sortino, F.

2002-03-01

We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits. The δ13CCO2 of the magmatic gases varies around -3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO2 concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (-1 to -‰ vs. standard mean ocean water [SMOW]), as well as the above δ13CCO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect. The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ13C of the entire hydrothermal system, including mixed H2O-CO2 vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and -2 to -6.5‰ vs. PDB for CO2. On these grounds, we think that Mediterranean marine water (δDH2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks

Calculation of intermolecular potentials for H2−H2 and H2−O2 dimers ab initio and prediction of second virial coefficients

International Nuclear Information System (INIS)

Pham Van, Tat; Deiters, Ulrich K.

2015-01-01

Highlights: • We construct the angular orientations of dimers H 2 −H 2 and H 2 −O 2 . • We calculate the ab initio intermolecular interaction energies for all built orientations. • Extrapolating the interaction energies to the complete basis set limit aug-cc-pV23Z. • We develop two 5-site ab initio intermolecular potentials of dimers H 2 −H 2 , H 2 −O 2 . • Calculating the virial coefficients of dimer H 2 −H 2 and H 2 −O 2 . - Abstract: The intermolecular interaction potentials of the dimers H 2 −H 2 and H 2 −O 2 were calculated from quantum mechanics, using coupled-cluster theory CCSD(T) and correlation-consistent basis sets aug-cc-pVmZ (m = 2, 3); the results were extrapolated to the basis set limit aug-cc-pV23Z. The interaction energies were corrected for the basis set superposition error with the counterpoise scheme. For comparison also Møller–Plesset perturbation theory (at levels 2–4) with the basis sets aug-cc-pVTZ were considered, but the results proved inferior. The quantum mechanical results were used to construct analytical pair potential functions. From these functions the second virial coefficients of hydrogen and the cross virial coefficients of the hydrogen–oxygen system were obtained by integration; in both cases corrections for quantum effects were included. The results agree well with experimental data, if available, or with empirical correlations

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

Science.gov (United States)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p biotechnology, medicine, chemistry and other areas.

Molybdenum isotope fractionation during adsorption to organic matter

Science.gov (United States)

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

2018-01-01

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

Patterns of predicted T-cell epitopes associated with antigenic drift in influenza H3N2 hemagglutinin.

Directory of Open Access Journals (Sweden)

E Jane Homan

Full Text Available Antigenic drift allowing escape from neutralizing antibodies is an important feature of transmission and survival of influenza viruses in host populations. Antigenic drift has been studied in particular detail for influenza A H3N2 and well defined antigenic clusters of this virus documented. We examine how host immunogenetics contributes to determination of the antibody spectrum, and hence the immune pressure bringing about antigenic drift. Using uTOPE™ bioinformatics analysis of predicted MHC binding, based on amino acid physical property principal components, we examined the binding affinity of all 9-mer and 15-mer peptides within the hemagglutinin 1 (HA1 of 447 H3N2 virus isolates to 35 MHC-I and 14 MHC-II alleles. We provide a comprehensive map of predicted MHC-I and MHC-II binding affinity for a broad array of HLA alleles for the H3N2 influenza HA1 protein. Each HLA allele exhibited a characteristic predicted binding pattern. Cluster analysis for each HLA allele shows that patterns based on predicted MHC binding mirror those described based on antibody binding. A single amino acid mutation or position displacement can result in a marked difference in MHC binding and hence potential T-helper function. We assessed the impact of individual amino acid changes in HA1 sequences between 10 virus isolates from 1968-2002, representative of antigenic clusters, to understand the changes in MHC binding over time. Gain and loss of predicted high affinity MHC-II binding sites with cluster transitions were documented. Predicted high affinity MHC-II binding sites were adjacent to antibody binding sites. We conclude that host MHC diversity may have a major determinant role in the antigenic drift of influenza A H3N2.

Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water.

Science.gov (United States)

Schultz, Natalie M; Griffis, Timothy J; Lee, Xuhui; Baker, John M

2011-11-15

Plant water extracts typically contain organic materials that may cause spectral interference when using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. Manufacturers of IRIS instruments have developed post-processing software to identify the degree of contamination in water samples, and potentially correct the isotope ratios of water with known contaminants. Here, the correction method proposed by an IRIS manufacturer, Los Gatos Research, Inc., was employed and the results were compared with those obtained from isotope ratio mass spectrometry (IRMS). Deionized water was spiked with methanol and ethanol to create correction curves for δ(18)O and δ(2)H. The contamination effects of different sample types (leaf, stem, soil) and different species from agricultural fields, grasslands, and forests were compared. The average corrections in leaf samples ranged from 0.35 to 15.73‰ for δ(2)H and 0.28 to 9.27‰ for δ(18)O. The average corrections in stem samples ranged from 1.17 to 13.70‰ for δ(2)H and 0.47 to 7.97‰ for δ(18)O. There was no contamination observed in soil water. Cleaning plant samples with activated charcoal had minimal effects on the degree of spectral contamination, reducing the corrections, by on average, 0.44‰ for δ(2)H and 0.25‰ for δ(18)O. The correction method eliminated the discrepancies between IRMS and IRIS for δ(18)O, and greatly reduced the discrepancies for δ(2)H. The mean differences in isotope ratios between IRMS and the corrected IRIS method were 0.18‰ for δ(18)O, and -3.39‰ for δ(2)H. The inability to create an ethanol correction curve for δ(2)H probably caused the larger discrepancies. We conclude that ethanol and methanol are the primary compounds causing interference in IRIS analyzers, and that each individual analyzer will probably require customized correction curves. Copyright © 2011 John Wiley & Sons, Ltd.

Inter- and intramolecular deuterium isotope effects on the cytochrome P-450-catalyzed oxidative dehalogenation of 1,1,2,2-tetrachloroethane

International Nuclear Information System (INIS)

Hales, D.B.; Ho, B.; Thompson, J.A.

1987-01-01

The oxidation of 1,1,2,2-tetrachloroethane to dichloroacetic acid was investigated with rat liver microsomes and purified cytochrome P-450. Deuterium substitution had no effect on Km values, but both the inter- and intramolecular isotope effects (kH/kD) on Vmax were in the range 5.7-6.1. The equivalence of the inter- and intramolecular values indicates that 6.0 may be a good estimate of the intrinsic isotope effect. The intermolecular kH/kD value for the conversion of 1,1,2,2-trichloroethane and its 1- 2 H analog to chloroacetic acid was 5.5. These data, and the finding that 1 atom of 18 O was incorporated into the product when TCEA was oxidized in an 18 O 2 atmosphere, support an oxidative dechlorination mechanism that involves hydrogen atom abstraction by the P-450 intermediate oxo complex

Novel proxies for reconstructing paleohydrology from ombrotrophic peatlands: biomarker and compound-specific H and C stable isotope ratios

Science.gov (United States)

Wang, J.; Nichols, J. E.; Huang, Y.

2008-12-01

Ombrotrophic peatlands are excellent archives for paleohydrologic information because they are hydrologically isolated from their surroundings. However, quantitative proxies for deciphering peatland archives are lacking. Here, we present development and application of novel organic geochemical methods for quantitative reconstruction of paleohydrology from the ombrotrophic sediments, and comparison of organic geochemical data with conventional paleoecological proxies. Application of these methods to the sediments of several North American and European peatlands has revealed significant changes in the hydroclimate throughout the Holocene. The plant assemblage living at the surface of the peatland is tightly controlled by surface moisture. Under wet conditions, Sphagnum mosses, with no active mechanism for drawing water from below the surface of the peatland, are dominant. During dry conditions, vascular plants are more productive relative to Sphagnum. A ratio of the abundance of two biomarkers representing Sphagnum and vascular plants sensitively records changes in hydrologic balance (Nichols et al., 2006, Org. Geochem. 37, 1505-1513). We have further developed stable isotope models to compute climate parameters from compound-specific H and C isotope ratios of biomarkers to create a more comprehensive climate reconstruction. Vascular plant leaf waxes carry the D/H ratio signature of precipitation that is little affected by evaporation, whereas the Sphagnum biomarker records isotopic ratios of the water at the peatland surface, which is strongly enriched by evaporation. Evaporation amount can be calculated using the differences between D/H ratios of the two types of biomarkers. C isotope ratios of Sphagnum biomarkers can also be used to quantify surface wetness. Methanotrophic bacteria live symbiotically with Sphagnum, providing isotopically light carbon for photosynthesis. These bacteria are more active when the Sphagnum is wet, thus providing more 13C-depleted CO2

Isotope effects in pericyclic reactions, ch. 2

International Nuclear Information System (INIS)

Dolbier, W.R. Jr.

1975-01-01

A distinction is made between primary and secondary isotope effects, the primary ones being based on the relative large vibrational frequencies and ensuing large zeroprint energies for C-H vibrations whereas the secondary effects are observed in systems where the vibrational modes of the isotopically labelled site are perturbed during transformation from reactant to product. Both effects are utilised in the elucidation of mechanism in pericyclic processes. The main processes dealt with in this chapter are cycloadditions of all types and sigmatropic rearrangements

2. Workshop 'Isotopes in Nature'. 1

International Nuclear Information System (INIS)

1979-11-01

The workshop was aimed at discussing in detail the following problems: (1) distribution of stable and radioactive isotopes in nature, (2) theoretical and experimental studies of isotopic effects in natural processes, (3) problems of sample preparation and sample measurement in determining the relative abundance of stable isotopes or radioactive isotopes in nature, (4) age estimations of samples from different areas of the geosphere, (5) contributions to the specification of global and regional substance cycles in nature with the aid of isotopic and geochemical studies. 75 summaries are included

Improve accuracy and sensibility in glycan structure prediction by matching glycan isotope abundance

International Nuclear Information System (INIS)

Xu Guang; Liu Xin; Liu Qingyan; Zhou Yanhong; Li Jianjun

2012-01-01

Highlights: ► A glycan isotope pattern recognition strategy for glycomics. ► A new data preprocessing procedure to detect ion peaks in a giving MS spectrum. ► A linear soft margin SVM classification for isotope pattern recognition. - Abstract: Mass Spectrometry (MS) is a powerful technique for the determination of glycan structures and is capable of providing qualitative and quantitative information. Recent development in computational method offers an opportunity to use glycan structure databases and de novo algorithms for extracting valuable information from MS or MS/MS data. However, detecting low-intensity peaks that are buried in noisy data sets is still a challenge and an algorithm for accurate prediction and annotation of glycan structures from MS data is highly desirable. The present study describes a novel algorithm for glycan structure prediction by matching glycan isotope abundance (mGIA), which takes isotope masses, abundances, and spacing into account. We constructed a comprehensive database containing 808 glycan compositions and their corresponding isotope abundance. Unlike most previously reported methods, not only did we take into count the m/z values of the peaks but also their corresponding logarithmic Euclidean distance of the calculated and detected isotope vectors. Evaluation against a linear classifier, obtained by training mGIA algorithm with datasets of three different human tissue samples from Consortium for Functional Glycomics (CFG) in association with Support Vector Machine (SVM), was proposed to improve the accuracy of automatic glycan structure annotation. In addition, an effective data preprocessing procedure, including baseline subtraction, smoothing, peak centroiding and composition matching for extracting correct isotope profiles from MS data was incorporated. The algorithm was validated by analyzing the mouse kidney MS data from CFG, resulting in the identification of 6 more glycan compositions than the previous annotation

C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site

Energy Technology Data Exchange (ETDEWEB)

Audí-Miró, Carme, E-mail: carmeaudi@ub.edu [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Cretnik, Stefan [Institute of Groundwater Ecology, Helmholtz Zentrum München-National Research Center for Environmental Health, Ingolstädter Landstrasse 1, D-85764 Neuherberg (Germany); Torrentó, Clara; Rosell, Mònica [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Shouakar-Stash, Orfan [Department of Earth & Environmental Sciences, 200 University Ave. W, N2L 3G1 Waterloo, Ontario (Canada); Otero, Neus [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Palau, Jordi [Université de Neuchâtel, CHYN - Centre d' Hydrogéologie, Rue Emile-Argand 11, CH-2000 Neuchâtel (Switzerland); and others

2015-12-15

Highlights: • {sup 13}C to evaluate natural chlorinated ethenes biodegradation. • {sup 13}C to evaluate the efficiency of a zero-valent iron-permeable reactive barrier. • {sup 13}C-{sup 37}Cl to discriminate biotic from abiotic degradation of cis-dichloroethene. • {sup 13}C-{sup 37}Cl-{sup 2}H of cis-DCE and TCE to elucidate different contaminant sources. - Abstract: Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using {sup 13}C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element {sup 13}C-{sup 37}Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using {sup 13}C-{sup 37}Cl-{sup 2}H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the {sup 13}C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual element {sup 13}C-{sup 37}Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respectively, were estimated to be removed by biodegradation. {sup 2}H combined with {sup 13}C and {sup 37}Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of δ{sup 2}H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation.

C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site

International Nuclear Information System (INIS)

Audí-Miró, Carme; Cretnik, Stefan; Torrentó, Clara; Rosell, Mònica; Shouakar-Stash, Orfan; Otero, Neus; Palau, Jordi

2015-01-01

Highlights: • 13 C to evaluate natural chlorinated ethenes biodegradation. • 13 C to evaluate the efficiency of a zero-valent iron-permeable reactive barrier. • 13 C- 37 Cl to discriminate biotic from abiotic degradation of cis-dichloroethene. • 13 C- 37 Cl- 2 H of cis-DCE and TCE to elucidate different contaminant sources. - Abstract: Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using 13 C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element 13 C- 37 Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using 13 C- 37 Cl- 2 H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the 13 C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual element 13 C- 37 Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respectively, were estimated to be removed by biodegradation. 2 H combined with 13 C and 37 Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of δ 2 H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation.

HERSCHEL/HIFI SEARCH FOR H{sub 2}{sup 17}O AND H{sub 2}{sup 18}O IN IRC+10216: CONSTRAINTS ON MODELS FOR THE ORIGIN OF WATER VAPOR

Energy Technology Data Exchange (ETDEWEB)

Neufeld, David A. [Department of Physics and Astronomy, Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218 (United States); Tolls, Volker; Melnick, Gary J. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Agundez, Marcelino [LAB, Universite de Bordeaux, UMR 5804, F-33270 Floirac (France); Gonzalez-Alfonso, Eduardo [Universidad de Alcala de Henares, Departamento de Fisica y Matematicas, Campus Universitario, E-28871 Alcala de Henares, Madrid (Spain); Decin, Leen [Instituut voor Sterrenkunde, Katholieke Universiteit Leuven, Celestijnenlaan 200D, 3001 Leuven (Belgium); Daniel, Fabien; Cernicharo, Jose [Departamento de Astrofisica, Centro de Astrobiologia, CSIC-INTA, Ctra. de Torrejon a Ajalvir km 4, E-28850 Madrid (Spain); Schmidt, Miroslaw; Szczerba, Ryszard [Nicolaus Copernicus Astronomical Center, Polish Academy of Sciences, Rabianska 8, 87-100 Torun (Poland)

2013-04-10

We report the results of a sensitive search for the minor isotopologues of water, H{sub 2}{sup 17}O and H{sub 2}{sup 18}O, toward the carbon-rich asymptotic giant branch star IRC+10216 (a.k.a. CW Leonis) using the HIFI instrument on the Herschel Space Observatory. This search was motivated by the fact that any detection of isotopic enhancement in the H{sub 2}{sup 17}O and H{sub 2}{sup 18}O abundances would have strongly implicated CO photodissociation as the source of the atomic oxygen needed to produce water in a carbon-rich circumstellar envelope. Our observations place an upper limit of 1/470 on the H{sub 2}{sup 17}O/H{sub 2}{sup 16}O abundance ratio. Given the isotopic {sup 17}O/{sup 16}O ratio of 1/840 inferred previously for the photosphere of IRC+10216, this result places an upper limit of a factor 1.8 on the extent of any isotope-selective enhancement of H{sub 2}{sup 17}O in the circumstellar material, and provides an important constraint on any model that invokes CO photodissociation as the source of O for H{sub 2}O production. In the context of the clumpy photodissociation model proposed previously for the origin of water in IRC+10216, our limit implies that {sup 12}C{sup 16}O (not {sup 13}C{sup 16}O or SiO) must be the dominant source of {sup 16}O for H{sub 2}O production, and that the effects of self-shielding can only have reduced the {sup 12}C{sup 16}O photodissociation rate by at most a factor {approx}2.

Mechanistic deductions from kinetic isotope effects and pH studies of pyridoxal phosphate dependent carbon-carbon lyases: Erwinia herbicola and Citrobacter freundii tyrosine phenol-lyase

International Nuclear Information System (INIS)

Kiick, D.M.; Phillips, R.S.

1988-01-01

The pH dependence of the kinetic parameters and primary deuterium isotope effects have been determined for tyrosine phenol-lyase from both Erwinia herbicola and Citrobacter freundii. The primary deuterium isotope effects indicate that proton abstraction from the 2-position of the substrate is partially rate-limiting for both enzymes. The C. freundii enzyme primary deuterium isotope effects [DV = 3.5 and D(V/Ktyr) = 2.5] are pH independent, indicating that tyrosine is not sticky (i.e., does not dissociate slower than it reacts to give products). Since Vmax for both tyrosine and the alternate substrate S-methyl-L-cysteine is also pH independent, substrate binds only to the correctly protonated form of the enzyme. For the E. herbicola enzyme, both Vmax and V/K for tyrosine or S-methyl-L-cysteine are pH dependent, as well as both DV and D(V/Ktyr). Thus, while both the protonated and unprotonated enzyme can bind substrate, and may be interconverted directly, only the unprotonated Michaelis complex is catalytically competent. At pH 9.5, DV = 2.5 and D(V/Ktyr) = 1.5. However, at pH 6.4 the isotope effect on both parameters is equal to 4.1. From these data, the forward commitment factor (cf = 5.2) and catalytic ratio (cvf = 1.1) for tyrosine and S-methyl-L-cysteine (cf = 2.2, cvf = 24) are calculated. Also, the Michaelis complex partition ratio (cf/cvf) for substrate and products is calculated to be 4.7 for tyrosine and 0.1 for S-methyl-L-cysteine

Deuterium isotope shifts for backbone {sup 1}H, {sup 15}N and {sup 13}C nuclei in intrinsically disordered protein {alpha}-synuclein

Energy Technology Data Exchange (ETDEWEB)

Maltsev, Alexander S.; Ying Jinfa; Bax, Ad, E-mail: bax@nih.gov [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

2012-10-15

Intrinsically disordered proteins (IDPs) are abundant in nature and characterization of their potential structural propensities remains a widely pursued but challenging task. Analysis of NMR secondary chemical shifts plays an important role in such studies, but the output of such analyses depends on the accuracy of reference random coil chemical shifts. Although uniform perdeuteration of IDPs can dramatically increase spectral resolution, a feature particularly important for the poorly dispersed IDP spectra, the impact of deuterium isotope shifts on random coil values has not yet been fully characterized. Very precise {sup 2}H isotope shift measurements for {sup 13}C{sup {alpha}}, {sup 13}C{sup {beta}}, {sup 13}C Prime , {sup 15}N, and {sup 1}H{sup N} have been obtained by using a mixed sample of protonated and uniformly perdeuterated {alpha}-synuclein, a protein with chemical shifts exceptionally close to random coil values. Decomposition of these isotope shifts into one-bond, two-bond and three-bond effects as well as intra- and sequential residue contributions shows that such an analysis, which ignores conformational dependence, is meaningful but does not fully describe the total isotope shift to within the precision of the measurements. Random coil {sup 2}H isotope shifts provide an important starting point for analysis of such shifts in structural terms in folded proteins, where they are known to depend strongly on local geometry.

The movement ecology of the straw-colored fruit bat, Eidolon helvum, in sub-Saharan Africa assessed by stable isotope ratios.

Directory of Open Access Journals (Sweden)

Gonzalo Ossa

Full Text Available Flying foxes (Pteropodidae are key seed dispersers on the African continent, yet their migratory behavior is largely unknown. Here, we studied the movement ecology of the straw-colored fruit bat, Eidolon helvum, and other fruit bats by analyzing stable isotope ratios in fur collected from museum specimens. In a triple-isotope approach based on samples of two ecologically similar non-migratory pteropodids, we first confirmed that a stable isotope approach is capable of delineating between geographically distinct locations in Sub-Saharan Africa. A discriminant function analysis assigned 84% of individuals correctly to their capture site. Further, we assessed how well hydrogen stable isotope ratios (δ(2H of fur keratin collected from non-migratory species (n = 191 individuals records variation in δ(2H of precipitation water in sub-Saharan Africa. Overall, we found positive, negative and no correlations within the six studied species. We then developed a reduced major axis regression equation based on individual data of non-migratory species to predict where potentially migratory E. helvum (n = 88 would come from based on their keratin δ(2H. Across non-migratory species, δ(2H of keratin and local water correlated positively. Based on the isoscape origin model, 22% of E. helvum were migratory, i.e. individuals had migrated over at least 250 km prior to their capture. Migratory individuals came from locations at a median distance of about 860 km from the collection site, four even from distances of at least 2,000 km. Ground-truthing of our isoscape origin model based on keratin δ(2H of extant E. helvum (n = 76 supported a high predictive power of assigning the provenance of African flying foxes. Our study highlights that stable isotope ratios can be used to explain the migratory behavior of flying foxes, even on the isotopically relatively homogenous African continent, and with material collected by museums many decades or more than a century ago.

The movement ecology of the straw-colored fruit bat, Eidolon helvum, in sub-Saharan Africa assessed by stable isotope ratios.

Science.gov (United States)

Ossa, Gonzalo; Kramer-Schadt, Stephanie; Peel, Alison J; Scharf, Anne K; Voigt, Christian C

2012-01-01

Flying foxes (Pteropodidae) are key seed dispersers on the African continent, yet their migratory behavior is largely unknown. Here, we studied the movement ecology of the straw-colored fruit bat, Eidolon helvum, and other fruit bats by analyzing stable isotope ratios in fur collected from museum specimens. In a triple-isotope approach based on samples of two ecologically similar non-migratory pteropodids, we first confirmed that a stable isotope approach is capable of delineating between geographically distinct locations in Sub-Saharan Africa. A discriminant function analysis assigned 84% of individuals correctly to their capture site. Further, we assessed how well hydrogen stable isotope ratios (δ(2)H) of fur keratin collected from non-migratory species (n = 191 individuals) records variation in δ(2)H of precipitation water in sub-Saharan Africa. Overall, we found positive, negative and no correlations within the six studied species. We then developed a reduced major axis regression equation based on individual data of non-migratory species to predict where potentially migratory E. helvum (n = 88) would come from based on their keratin δ(2)H. Across non-migratory species, δ(2)H of keratin and local water correlated positively. Based on the isoscape origin model, 22% of E. helvum were migratory, i.e. individuals had migrated over at least 250 km prior to their capture. Migratory individuals came from locations at a median distance of about 860 km from the collection site, four even from distances of at least 2,000 km. Ground-truthing of our isoscape origin model based on keratin δ(2)H of extant E. helvum (n = 76) supported a high predictive power of assigning the provenance of African flying foxes. Our study highlights that stable isotope ratios can be used to explain the migratory behavior of flying foxes, even on the isotopically relatively homogenous African continent, and with material collected by museums many decades or more than a century ago.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

Science.gov (United States)

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

2018-02-01

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

Repositioning the substrate activity screening (SAS) approach as a fragment-based method for identification of weak binders.

Science.gov (United States)

Gladysz, Rafaela; Cleenewerck, Matthias; Joossens, Jurgen; Lambeir, Anne-Marie; Augustyns, Koen; Van der Veken, Pieter

2014-10-13

Fragment-based drug discovery (FBDD) has evolved into an established approach for "hit" identification. Typically, most applications of FBDD depend on specialised cost- and time-intensive biophysical techniques. The substrate activity screening (SAS) approach has been proposed as a relatively cheap and straightforward alternative for identification of fragments for enzyme inhibitors. We have investigated SAS for the discovery of inhibitors of oncology target urokinase (uPA). Although our results support the key hypotheses of SAS, we also encountered a number of unreported limitations. In response, we propose an efficient modified methodology: "MSAS" (modified substrate activity screening). MSAS circumvents the limitations of SAS and broadens its scope by providing additional fragments and more coherent SAR data. As well as presenting and validating MSAS, this study expands existing SAR knowledge for the S1 pocket of uPA and reports new reversible and irreversible uPA inhibitor scaffolds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen constituents of the mesosphere inferred from positive ions - H2O, CH4, H2CO, H2O2, and HCN

Science.gov (United States)

Kopp, E.

1990-01-01

The concentrations in the mesosphere of H2O, CH4, H2CO, H2O2, and HCN were inferred from data on positive ion compositions, obtained from one mid-latitude and four high-latitude rocket flights. The inferred concentrations were found to agree only partially with the ground-based microwave measurements and/or model prediction by Garcia and Solomon (1985). The CH4 concentration was found to vary between 70 and 4 ppb in daytime and 900 and 100 ppbv at night, respectively. Unexpectedly high H2CO concentrations were obtained, with H2CO/H2O ratios between 0.0006 and 0.1, and a mean HCN volume mixing ratio of 6 x 10 to the -10th was inferred.

Shell-model-based deformation analysis of light cadmium isotopes

Science.gov (United States)

Schmidt, T.; Heyde, K. L. G.; Blazhev, A.; Jolie, J.

2017-07-01

Large-scale shell-model calculations for the even-even cadmium isotopes 98Cd-108Cd have been performed with the antoine code in the π (2 p1 /2;1 g9 /2) ν (2 d5 /2;3 s1 /2;2 d3 /2;1 g7 /2;1 h11 /2) model space without further truncation. Known experimental energy levels and B (E 2 ) values could be well reproduced. Taking these calculations as a starting ground we analyze the deformation parameters predicted for the Cd isotopes as a function of neutron number N and spin J using the methods of model independent invariants introduced by Kumar [Phys. Rev. Lett. 28, 249 (1972), 10.1103/PhysRevLett.28.249] and Cline [Annu. Rev. Nucl. Part. Sci. 36, 683 (1986), 10.1146/annurev.ns.36.120186.003343].

CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

Science.gov (United States)

Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

2017-09-01

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three

Utilization of stable isotopes for characterizing an underground gas generator

International Nuclear Information System (INIS)

Pirard, J.P.; Antenucci, D.; Renard, X.; Letolle, R.

1994-01-01

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O 2 , H 2 O) and in the effluent (CO 2 , CO, H 2 , H 2 O, CH 4 , O 2 , heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs

Validity of Simpson-Angus Scale (SAS) in a naturalistic schizophrenia population.

Science.gov (United States)

Janno, Sven; Holi, Matti M; Tuisku, Katinka; Wahlbeck, Kristian

2005-03-17

Simpson-Angus Scale (SAS) is an established instrument for neuroleptic-induced parkinsonism (NIP), but its statistical properties have been studied insufficiently. Some shortcomings concerning its content have been suggested as well. According to a recent report, the widely used SAS mean score cut-off value 0.3 of for NIP detection may be too low. Our aim was to evaluate SAS against DSM-IV diagnostic criteria for NIP and objective motor assessment (actometry). Ninety-nine chronic institutionalised schizophrenia patients were evaluated during the same interview by standardised actometric recording and SAS. The diagnosis of NIP was based on DSM-IV criteria. Internal consistency measured by Cronbach's alpha, convergence to actometry and the capacity for NIP case detection were assessed. Cronbach's alpha for the scale was 0.79. SAS discriminated between DSM-IV NIP and non-NIP patients. The actometric findings did not correlate with SAS. ROC-analysis yielded a good case detection power for SAS mean score. The optimal threshold value of SAS mean score was between 0.65 and 0.95, i.e. clearly higher than previously suggested threshold value. We conclude that SAS seems a reliable and valid instrument. The previously commonly used cut-off mean score of 0.3 has been too low resulting in low specificity, and we suggest a new cut-off value of 0.65, whereby specificity could be doubled without loosing sensitivity.

Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO{sub 2} nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Piro, M.H.A., E-mail: markuspiro@gmail.com [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Banfield, J. [Nuclear Engineering Department, University of Tennessee, Knoxville, TN (United States); Clarno, K.T., E-mail: clarnokt@ornl.gov [Reactor and Nuclear Systems Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Simunovic, S. [Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Besmann, T.M. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Lewis, B.J.; Thompson, W.T. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON (Canada)

2013-10-15

Predictive capabilities for simulating irradiated nuclear fuel behavior are enhanced in the current work by coupling thermochemistry, isotopic evolution and heat transfer. Thermodynamic models that are incorporated into this framework not only predict the departure from stoichiometry of UO{sub 2}, but also consider dissolved fission and activation products in the fluorite oxide phase, noble metal inclusions, secondary oxides including uranates, zirconates, molybdates and the gas phase. Thermochemical computations utilize the spatial and temporal evolution of the fission and activation product inventory in the pellet, which is typically neglected in nuclear fuel performance simulations. Isotopic computations encompass the depletion, decay and transmutation of more than 2000 isotopes that are calculated at every point in space and time. These computations take into consideration neutron flux depression and the increased production of fissile plutonium near the fuel pellet periphery (i.e., the so-called “rim effect”). Thermochemical and isotopic predictions are in very good agreement with reported experimental measurements of highly irradiated UO{sub 2} fuel with an average burnup of 102 GW d t(U){sup −1}. Simulation results demonstrate that predictions are considerably enhanced when coupling thermochemical and isotopic computations in comparison to empirical correlations. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

Cerebral scintigraphy by 99mTc-HMPAO in sleep apnea syndromes (SAS) during the wakeful state

International Nuclear Information System (INIS)

Tainturier, C.; Benamor, M.; Hausser-Hauw, C.; Rakotonanahary, D.; Fleury, B.

1997-01-01

The SAS is associated to cerebral hemodynamic modifications and to a high frequency of cerebro-vascular accidents. The aim of this study was to verify, during wakeful state, the cerebral hemodynamic in 14 patients afflicted with SAS of various intensity (Apnea Index = 5-120/h). 555 MBq of 99m Tc-HMPAO were injected in patients maintained awake. The images were obtained 20 minutes after injection by mean of a double-head chamber equipped with fan-beam collimators. They were interpreted visually by two independent readers. Anomalies of cerebral fixation were observed in 12/14 patients. They were small sores of diffuse hypo-fixations, with a 'riddly' aspect (4 cases), sores of bi-temporal hypo-fixation with a right- or left- hemispheric predominance (6 cases), or right fronto-temporal hypo-fixations (2 cases). The cerebral fixation anomalies were reported in the SASs. Ficker et al (1997) have shown in-sleep frontal hypo-perfusions in 5/14 apneic patients, reversible under continuous positive airing pressure (CPAP). In conclusion, anomalies of cerebral fixation exist in SAS-carrying patients, even in the wakeful state. Questions about hypoperfusion, pre-lacunar syndrome, atrophy still remain. A check of this study is planned after the CPAP treatment to determine the hemodynamic or anatomic origin and the anomaly reversibility

Density functional theory calculations of H/D isotope effects on polymer electrolyte membrane fuel cell operations

Energy Technology Data Exchange (ETDEWEB)

Yanase, Satoshi; Oi, Takao [Sophia Univ., Tokyo (Japan). Faculty of Science and Technology

2015-10-01

To elucidate hydrogen isotope effects observed between fuel and exhaust hydrogen gases during polymer electrolyte membrane fuel cell operations, H-to-D reduced partition function ratios (RPFRs) for the hydrogen species in the Pt catalyst phase of the anode and the electrolyte membrane phase of the fuel cell were evaluated by density functional theory calculations on model species of the two phases. The evaluation yielded 3.2365 as the value of the equilibrium constant of the hydrogen isotope exchange reaction between the two phases at 39 C, which was close to the experimentally estimated value of 3.46-3.99 at the same temperature. It was indicated that H{sup +} ions on the Pt catalyst surface of the anode and H species in the electrolyte membrane phase were isotopically in equilibrium with one another during fuel cell operations.

Production of Long-Lived H2-, HD-, and D2- during Grazing Scattering Collisions of H2+, H3+, D2+, D3+ and D2H+ Ions with KBr, KCl, and LiF Surfaces

International Nuclear Information System (INIS)

Seely, D. G.; Meyer, F. W.; Zhang, H.; Havener, C. C.

2009-01-01

We have investigated atomic and molecular anion production from singly charged atomic and molecular hydrogen, deuterium, and mixed isotope beams during grazing interactions with large area KBr, KCl, and LiF single crystal targets in the incident energy range 4-22.5 keV. Electron capture and, in the case of incident molecular ions, dissociation occur during the grazing interactions without appreciable angular straggling or change in velocity. As a result, atomic and molecular cation and anion interaction products are strongly peaked in the specular reflection direction, and, in case of dissociation products, at the fractional kinetic energies determined by the product fragment mass to incident mass ratios. A large-acceptance electrostatic analysis and detection system is used to collect the charged scattering products with high efficiency. Of particular interest is the production of metastable molecular ions H 2 - , HD - , and D 2 - . By comparing molecular anion yields obtained from incident hydrogen, deuterium and mixed isotope molecular ions, effects arising from isobaric contamination are seen for some incident molecular species.

Method of preparing mercury with an arbitrary isotopic distribution

Science.gov (United States)

Grossman, M.W.; George, W.A.

1986-12-16

This invention provides for a process for preparing mercury with a predetermined, arbitrary, isotopic distribution. In one embodiment, different isotopic types of Hg[sub 2]Cl[sub 2], corresponding to the predetermined isotopic distribution of Hg desired, are placed in an electrolyte solution of HCl and H[sub 2]O. The resulting mercurous ions are then electrolytically plated onto a cathode wire producing mercury containing the predetermined isotopic distribution. In a similar fashion, Hg with a predetermined isotopic distribution is obtained from different isotopic types of HgO. In this embodiment, the HgO is dissolved in an electrolytic solution of glacial acetic acid and H[sub 2]O. The isotopic specific Hg is then electrolytically plated onto a cathode and then recovered. 1 fig.

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

Science.gov (United States)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

[Analysis of hydrogen isotopes by gas chromatography using a MnCl2 coated γ-Al2O3 capillary packed column].

Science.gov (United States)

Chen, Ping; Fu, Xiaolong; Hu, Peng; Xiao, Chengjian; Ren, Xingbi; Xia, Xiulong; Wang, Heyi

2017-07-08

The conventional packed column gas chromatographic analysis of hydrogen isotopes has low column efficiency, broad peak and long retention time. In this work, a γ -Al 2 O 3 with MnCl 2 coated capillary packed column was tested at cryogenic temperature. The systematic column efficiency analysis and the hydrogen isotopes analytical technique research had been carried out. The results showed that, the γ -Al 2 O 3 with MnCl 2 coating could greatly improve the surface degree of order, pore structure and adsorption properties. Also the o -H 2 peak and p -H 2 peak were eluted in a single area. The γ -Al 2 O 3 with MnCl 2 coating was packed into a 0.53 mm inner diameter and 1.0 m long fused silica capillary column. It had a good linear relationship used this column with thermal conductivity detector (TCD) to detect the volume concentrations of hydrogen isotopes from 1 to 10 mL/L, and the relative error was less than 5% for low concentration sample testing. For H 2 , HD and D 2 , the retention times can be shortened to 39, 46 and 60 s, respectively. The limits of detection were reduced to 0.046, 0.067 and 0.072 mL/L, respectively. Compared with conventional packed column, capillary packed column had sharper peak form, higher separation degree of adjacent components, shorter retention time and lower detection limits. The above results indicate that the capillary packed column with TCD detector can be used for fast detection of low concentration of hydrogen isotopes and their online analysis.

Isotope ratio in stellar atmospheres and nucleosynthesis

International Nuclear Information System (INIS)

Barbuy, B.L.S.

1987-01-01

The determination of isotopic ratios in stellar atmospheres is studied. The isotopic shift of atomic and molecular lines of different species of a certain element is examined. CH and MgH lines are observed in order to obtain the 12 C: 13 C and 24 Mg: 25 Mg: 26 Mg isotpic ratios. The formation of lines in stellar atmospheres is computed and the resulting synthetic spectra are employed to determine the isotopic abundances. The results obtained for the isotopic ratios are compared to predictions of nucleosynthesis theories. Finally, the concept of primary and secondary element is discussed, and these definitions are applied to the observed variations in the abundance of elements as a function of metallicity. (author) [pt

Cerebral scintigraphy by {sup 99m}Tc-HMPAO in sleep apnea syndromes (SAS) during the wakeful state; Scintigraphie cerebrale au Tc99m-HMPAO dans les syndromes d`apnees du sommeil (SAS) pendant l`etat de veille

Energy Technology Data Exchange (ETDEWEB)

Tainturier, C.; Benamor, M.; Hausser-Hauw, C.; Rakotonanahary, D.; Fleury, B. [CMC FOCH 92150 SURESNES (France)

1997-12-31

The SAS is associated to cerebral hemodynamic modifications and to a high frequency of cerebro-vascular accidents. The aim of this study was to verify, during wakeful state, the cerebral hemodynamic in 14 patients afflicted with SAS of various intensity (Apnea Index = 5-120/h). 555 MBq of {sup 99m}Tc-HMPAO were injected in patients maintained awake. The images were obtained 20 minutes after injection by mean of a double-head chamber equipped with fan-beam collimators. They were interpreted visually by two independent readers. Anomalies of cerebral fixation were observed in 12/14 patients. They were small sores of diffuse hypo-fixations, with a `riddly` aspect (4 cases), sores of bi-temporal hypo-fixation with a right- or left- hemispheric predominance (6 cases), or right fronto-temporal hypo-fixations (2 cases). The cerebral fixation anomalies were reported in the SASs. Ficker et al (1997) have shown in-sleep frontal hypo-perfusions in 5/14 apneic patients, reversible under continuous positive airing pressure (CPAP). In conclusion, anomalies of cerebral fixation exist in SAS-carrying patients, even in the wakeful state. Questions about hypoperfusion, pre-lacunar syndrome, atrophy still remain. A check of this study is planned after the CPAP treatment to determine the hemodynamic or anatomic origin and the anomaly reversibility

5-Hydroxypyrido[2,3-b]pyrazin-6(5H)-one derivatives as novel dual inhibitors of HIV-1 reverse transcriptase-associated ribonuclease H and integrase.

Science.gov (United States)

Sun, Lin; Gao, Ping; Dong, Guanyu; Zhang, Xujie; Cheng, Xiqiang; Ding, Xiao; Wang, Xueshun; Daelemans, Dirk; De Clercq, Erik; Pannecouque, Christophe; Menéndez-Arias, Luis; Zhan, Peng; Liu, Xinyong

2018-06-18

We reported herein the design, synthesis and biological evaluation of a series of 5-hydroxypyrido[2,3-b]pyrazin-6(5H)-one derivatives as HIV-1 reverse transcriptase (RT) ribonuclease H (RNase H) inhibitors using a privileged structure-guided scaffold refining strategy. In view of the similarities between the pharmacophore model of RNase H and integrase (IN) inhibitors as well as their catalytic sites, we also performed IN inhibition assays. Notably, the majority of these derivatives inhibited RNase H and IN at micromolar concentrations. Among them, compound 7a exhibited similar inhibitory activity against RNase H and IN (IC 50 RNase H  = 1.77 μM, IC 50 IN  = 1.18 μM, ratio = 1.50). To the best of our knowledge, this is the first reported dual HIV-1 RNase H-IN inhibitor based on a 5-hydroxypyrido[2,3-b]pyrazin-6(5H)-one structure. Molecular modeling has been used to predict the binding mode of 7a in complex with the catalytic cores of HIV-1 RNase H and IN. Taken together these results strongly support the feasibility of developing HIV-1 dual inhibitors from analog-based optimization of divalent metal ion chelators. Recently, the identification of dual inhibitors proved to be a highly effective strategy for novel antivirals discovery. Therefore, these compounds appear to be useful leads that can be further modified to develop more valuable anti-HIV-1 molecules with suitable drug profiles. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Validity of Simpson-Angus Scale (SAS in a naturalistic schizophrenia population

Directory of Open Access Journals (Sweden)

Tuisku Katinka

2005-03-01

Full Text Available Abstract Background Simpson-Angus Scale (SAS is an established instrument for neuroleptic-induced parkinsonism (NIP, but its statistical properties have been studied insufficiently. Some shortcomings concerning its content have been suggested as well. According to a recent report, the widely used SAS mean score cut-off value 0.3 of for NIP detection may be too low. Our aim was to evaluate SAS against DSM-IV diagnostic criteria for NIP and objective motor assessment (actometry. Methods Ninety-nine chronic institutionalised schizophrenia patients were evaluated during the same interview by standardised actometric recording and SAS. The diagnosis of NIP was based on DSM-IV criteria. Internal consistency measured by Cronbach's α, convergence to actometry and the capacity for NIP case detection were assessed. Results Cronbach's α for the scale was 0.79. SAS discriminated between DSM-IV NIP and non-NIP patients. The actometric findings did not correlate with SAS. ROC-analysis yielded a good case detection power for SAS mean score. The optimal threshold value of SAS mean score was between 0.65 and 0.95, i.e. clearly higher than previously suggested threshold value. Conclusion We conclude that SAS seems a reliable and valid instrument. The previously commonly used cut-off mean score of 0.3 has been too low resulting in low specificity, and we suggest a new cut-off value of 0.65, whereby specificity could be doubled without loosing sensitivity.

Sulfur and selenium isotope separation by distillation

International Nuclear Information System (INIS)

Mills, T. R.; McInteer, B. B.; Montoya, J. G.

1988-01-01

Sulfur and selenium isotopes are used for labeled compounds and as precursors for radioisotope production; however, both limited availability and high costs are problems. A new method is needed for large-scale separation of these isotopes. Experimental distillation columns were used to measure isotopic separations for sulfur and selenium compounds. The maximum total isotope separation of 32 S vs. 34 S were 1.127 for H 2 S, 1.048 for COS, 0.838 for SF 4 , and 1.058 for CH 3 SH. Relative volatilities of 32 S vs. 34 S are 1.0006 for COS and 0.9976 for SF 4 . There is a reverse isotope effect for carbon in COS. No isotopic separation was observed for dimethyl selenide. The lower mass selenium isotopes in H 2 Se are more volatile. Distillation is a promising method for separating sulfur isotopes on a production scale. Existing distillation technology produced separated isotopes with an effect similar to that found for sulfur in SF 4 . 8 refs., 2 tabs

Sulfur and selenium isotope separation by distillation

International Nuclear Information System (INIS)

Mills, T.R.; McInteer, B.B.; Montoya, J.G.

1989-01-01

Sulfur and selenium isotopes are used for labeled compounds and as precursors for radioisotope production; however, both limited availability and high costs are problems. A new method is needed for large-scale separation of theses isotopes. Experimental distillation columns were used to measure isotopic separations for sulfur and selenium compounds. The maximum total isotope separations of 32 S vs. 34 S were 1.127 for H 2 S, 1.048 for COS, 0.838 for SF 4 , and 1.058 for CH 3 SH. Relative volatilities of 32 S and 34 S are 1.0006 for COS and 0.9976 for SF 4 . There is a reverse isotope effect for carbon in COS. No isotopic separation was observed for dimethyl selenide. The lower mass selenium isotopes in H 2 Se are more volatile. Distillation is a promising method for separating sulfur isotopes on a production scale. Existing distillation technology produces separated isotopes with an effect similar to that found for sulfur in SF 4 . (author). 8 refs.; 2 tabs

SAS3DC - A computer program to describe accidents in LMFBRs

International Nuclear Information System (INIS)

Angerer, G.; Arnecke, G.; Polch, A.

1981-02-01

The code system SAS3D - developed in the ANL - is at present the most adequate instrument for simulating accidents in the LMFBRs. SAS3DC is an improved version of this code system: the routine CLAZAS - modelling in SAS3D the motion of the fuel cladding - is replaced in the SAS3DC by the routine CMOT. CMOT describes the moving material not in the Lagrangian - as CLAZAS - but in the Eulerian system and is so able to register even small cladding-displacements. To complete the description of the SAS3DC-code the results of some sample problems are included. (orig.) [de

Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

International Nuclear Information System (INIS)

Uda, Tatsuhiko

1992-01-01

Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

[Standardization of the Greek version of Zung's Self-rating Anxiety Scale (SAS)].

Science.gov (United States)

Samakouri, M; Bouhos, G; Kadoglou, M; Giantzelidou, A; Tsolaki, K; Livaditis, M

2012-01-01

Self-rating Anxiety Scale (SAS), introduced by Zung, has been widely used in research and in clinical practice for the detection of anxiety. The present study aims at standardizing the Greek version of SAS. SAS consists of 20 items rated on a 1-4 likert type scale. The total SAS score may vary from 20 (no anxiety at all) to 80 (severe anxiety). Two hundred and fifty four participants (114 male and 140 female), psychiatric patients, physically ill and general population individuals, aged 45.40±11.35 years, completed the following: (a) a demographic characteristics' questionnaire, (b) the SAS Greek version, (c) the Spielberg's Modified Greek State-Trait Anxiety Scale (STAI-Gr.-X) and (d) the Zung Depression Rating Scale (ZDRS). Seventy six participants answered the SAS twice within a 12th-day median period of time. The following parameters were calculated: (a) internal consistency of the SAS in terms of Cronbach's α co-efficient, (b) its test-retest reliability in terms of the Intraclass Correlation Coefficient (ICC) and (c) its concurrent and convergent validities through its score's Spearman's rho correlations with both the state and trait subscales of STAI-Gr X and the ZDRS. In addition, in order to evaluate SAS' discriminant validity, the scale's scores of the three groups of participants (psychiatric patients, physically ill and general population individuals) were compared among each other, in terms of Kruskall Wallis and Mann Whitney U tests. SAS Cronbach's alpha equals 0.897 while ICC regarding its test-retest reliability equals 0.913. Spearman's rho concerning validity: (a) when SAS is compared to STAI-Gr.-X (state), equals it 0.767, (b) when SAS is compared to STAI-Gr. X (trait), it equals 0.802 and (c) when SAS is compared to ZDRS, it equals 0.835. The mentally ill scored significantly higher in SAS compared to both the healthy and the general population. In conclusion, the SAS Greek version presents very satisfactory psychometric properties regarding

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

Science.gov (United States)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

Ion-molecule interactions in crossed-beams. [N/sup +/-H/sub 2/; F/sup +/-H; CO/sub 2//sup +/-D/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Hansen, S.G.

1980-09-01

Interactions of the ions N/sup +/, F/sup +/, and CO/sub 2//sup +/ with H/sub 2/ and/or its isotopes were examined using the crossed-beam technique in the low (< 4 eV) initial relative energy. For the reaction N/sup +/(/sup 3/P) + H/sub 2/ ..-->.. NH/sup +/ + H, complex formation dominates up to 1.9 eV and a substantial interaction occurs between all collision partners up to 3.6 eV. The distribution of N/sup +/ scattered nonreactively from H/sub 2/ also showed a long-lived complex channel below 1.9 eV. The reaction F/sup +/(/sup 3/P) + H/sub 2/ ..-->..FH/sup +/ + H proceeded by a direct reaction mechanism at 0.20 to 1.07 eV. The reaction CO/sub 2//sup +/ + D/sub 2/ ..-->.. DCO/sub 2//sup +/ + D gives asymmetric product distributions at 0.27 eV and above, indicating a direct reaction mechanism. Results indicated that there are probably barriers in the exit channels for DCO/sub 2//sup +/, DCO/sup +/, and D/sub 2/O/sup +/ products. The electronic state distributions of the N/sup +/, F/sup +/, and CO/sub 2//sup +/ beams was investigated using beam attenuation and total luminescence techniques.

Isotopic geothermometers in geothermal areas. A comparative experimental study in Larderella, Italy

International Nuclear Information System (INIS)

Nuti, S.; Panichi, C.

1979-06-01

The stable isotope composition of some geothermal fluid components has been determined in view of evaluating the temperature at depth in Italian geothermal fields (Larderello, Mt. Amiata, Travale). The isotopic systems used are: 13 C(CO 2 -CH 4 ), 18 O(CO 2 -H 2 O), D(H 2 -CH 4 ) and D(H 2 O-H 2 ), for which the isotopic equilibrium variation with temperature are known either experimentally or theoretically. The 18 O(CO 2 -H 2 O) geothermometer gives temperatures similar to those observed at the well-head, and provides therefore useful information on the physical state of water (steam or evaporating liquid water) at the well bottom. On the contrary, all other geothermometers produce too high temperatures which can be explained by incomplete equilibration or lack of equilibrium between components and, perhaps in some cases, by the insufficient knowledge of the fractionation factors. The comparison between the different isotopic geothermometers, along with some chemical and physico-chemical evidence, suggests that the reaction already proposed, i.e. CO 2 +4H 2 =CH 4 +2H 2 O, is unable to explain the isotopic composition observed. On the contrary, the water dissociation reaction (H 2 O=H 2 +1/2O 2 ) and the synthesis reaction of methane (C+2H 2 =CH 4 ) and carbon dioxide (C+O 2 =CO 2 ) seem able to provide an appropriate explanation of the isotopic behaviour of the geothermal field fluid components

SAS and R data management, statistical analysis, and graphics

CERN Document Server

Kleinman, Ken

2009-01-01

An All-in-One Resource for Using SAS and R to Carry out Common TasksProvides a path between languages that is easier than reading complete documentationSAS and R: Data Management, Statistical Analysis, and Graphics presents an easy way to learn how to perform an analytical task in both SAS and R, without having to navigate through the extensive, idiosyncratic, and sometimes unwieldy software documentation. The book covers many common tasks, such as data management, descriptive summaries, inferential procedures, regression analysis, and the creation of graphics, along with more complex applicat

Equation-of-state for fluids at high densities-hydrogen isotope measurements and thermodynamic derivations

International Nuclear Information System (INIS)

Liebenberg, D.H.; Mills, R.L.; Bronson, J.C.

1977-01-01

Hydrogen isotopes play an important role in energy technologies, in particular, the compression to high densities for initiation of controlled thermonuclear fusion energy. At high densities the properties of the compressed hydrogen isotopes depart drastically from ideal thermodynamic predictions. The measurement of accurate data including the author's own recent measurements of n-H 2 and n-D 2 in the range 75 to 300 K and 0.2 to 2.0 GPa (2 to 20 kbar) is reviewed. An equation-of-state of the Benedict type is fit to these data with a double-process least-squares computer program. The results are reviewed and compared with existing data and with a variety of theoretical work reported for fluid hydrogens. A new heuristic correlation is presented for simplicity in predicting volumes and sound velocity at high pressures. 9 figures, 1 table

Infrared spectra of 4HeH+, 4HeD+, 3HeH+, and 3HeD+

International Nuclear Information System (INIS)

Crofton, M.W.; Altman, R.S.; Haese, N.N.; Oka, T.

1989-01-01

Isotopic species of the HeH + molecular ion provide an excellent testing ground for studying isotopic dependence of vibration--rotation constants because of the small masses of He and H isotopes. We have observed infrared spectra of the hot band v=2 left-arrow 1 of HeH + and fundamental bands of isotopic species HeD + , 3 HeH + , and 3 HeD + , and obtained the Dunham coefficients Y kl , and the isotopically independent parameters U kl , Δ He kl , and Δ H kl

Spanish Network for Isotopes in Precipitation: Isotope Spatial distribution and contribution to the knowledge of the hydrological cycle

International Nuclear Information System (INIS)

Diaz-Teijeiro, M. F.; Rodriguez-Arevalo, J.; Castano, S.

2009-01-01

The results of seven years of operation of the Spanish Network for Isotopes ( 2 H, 1 8O y 3 H) in Precipitation (REVIP) are shown. this Network is managed since 2000 by the Centro de Estudios de Tecnicas Aplicadas of the Centro de Estudios y Experimentacion de Obras Publicas (CEDEX) in collaboration with the Agencia Estatal de Meteorologia (AEMET). The results of REVIP are sent to the International Atomic Energy Agency (IAEA) in order to be integrated in the Global Network for Isotopes in Precipitation (GNIP). The spatial distribution of stable isotopes ( 1 8O h 2 H) in precipitation in Spain follows a multiple regression model, based on two geographic factors: latitude and elevation, which is strongly correlated with temperature, an important factor controlling isotope fractionation. This information on 1 8O and 2 H is useful to trace surface and ground waters and, combined with the information, about the spatial and temporal distribution of the Tritium ( 3 H) concentration in precipitation, allows to date these waters in order to estimate flow directions and velocities, and to evaluate the residence time of water resources and aquifer vulnerability. (Author)

13CO2/12CO2 isotope ratio analysis in human breath using a 2 μm diode laser

Science.gov (United States)

Sun, Mingguo; Cao, Zhensong; Liu, Kun; Wang, Guishi; Tan, Tu; Gao, Xiaoming; Chen, Weidong; Yinbo, Huang; Ruizhong, Rao

2015-04-01

The bacterium H. pylori is believed to cause peptic ulcer. H. pylori infection in the human stomach can be diagnosed through a CO2 isotope ratio measure in exhaled breath. A laser spectrometer based on a distributed-feedback semiconductor diode laser at 2 μm is developed to measure the changes of 13CO2/12CO2 isotope ratio in exhaled breath sample with the CO2 concentration of ~4%. It is characterized by a simplified optical layout, in which a single detector and associated electronics are used to probe CO2 spectrum. A new type multi-passes cell with 12 cm long base length , 29 m optical path length in total and 280 cm3 volume is used in this work. The temperature and pressure are well controlled at 301.15 K and 6.66 kPa with fluctuation amplitude of 25 mK and 6.7 Pa, respectively. The best 13δ precision of 0.06o was achieved by using wavelet denoising and Kalman filter. The application of denoising and Kalman filter not only improved the signal to noise ratio, but also shorten the system response time.

Pharmaceuticals labelled with stable isotopes

International Nuclear Information System (INIS)

Krumbiegel, P.

1986-11-01

The relatively new field of pharmaceuticals labelled with stable isotopes is reviewed. Scientific, juridical, and ethical questions are discussed concerning the application of these pharmaceuticals in human medicine. 13 C, 15 N, and 2 H are the stable isotopes mainly utilized in metabolic function tests. Methodical contributions are given to the application of 2 H, 13 C, and 15 N pharmaceuticals showing new aspects and different states of development in the field under discussion. (author)

Stable Oxygen-18 and Deuterium Isotopes

DEFF Research Database (Denmark)

Müller, Sascha

The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

Mirror suspension system for the TAMA SAS

CERN Document Server

Takamori, A; Bertolini, A; Cella, G; DeSalvo, R; Fukushima, M; Iida, Y; Jacquier, F; Kawamura, S; Marka, S; Nishi, Y; Numata, K; Sannibale, V; Somiya, K; Takahashi, R; Tariq, H; Tsubono, K; Ugas, J; Viboud, N; Yamamoto, H; Yoda, T; Wang Chen Yang

2002-01-01

Several R and D programmes are ongoing to develop the next generation of interferometric gravitational wave detectors providing the superior sensitivity desired for refined astronomical observations. In order to obtain a wide observation band at low frequencies, the optics need to be isolated from the seismic noise. The TAMA SAS (seismic attenuation system) has been developed within an international collaboration between TAMA, LIGO, and some European institutes, with the main objective of achieving sufficient low-frequency seismic attenuation (-180 dB at 10 HZ). The system suppresses seismic noise well below the other noise levels starting at very low frequencies above 10 Hz. It also includes an active inertial damping system to decrease the residual motion of the optics enough to allow a stable operation of the interferometer. The TAMA SAS also comprises a sophisticated mirror suspension subsystem (SUS). The SUS provides support for the optics and vibration isolation complementing the SAS performance. The SU...

Syngas (CO-H2) production using high temperature micro-tubular solid oxide electrolysers

International Nuclear Information System (INIS)

Kleiminger, L.; Li, T.; Li, K.; Kelsall, G.H.

2015-01-01

Highlights: • CO 2 and/or H 2 O reduced to CO/H 2 in micro-tubular solid oxide electrolyser (MT-SOE). • MT-SOE: CO 2 , H 2 O | Ni-(ZrO 2 ) 0.92 (Y 2 O 3 ) 0.08 (YSZ) | YSZ | YSZ- La 0.8 Sr 0.2 MnO 3-δ |O 2. • −0.76 A cm −2 achieved at 1.5V and ca. 820°C for H 2 O electrolysis. • Ni wire cathode current collector gave better performance than (Ag wire+Ag paste). • C 18 O 2 in co-electrolysis could not distinguish cathodic and chemical reduction. - Abstract: CO 2 and/or H 2 O were reduced to CO/H 2 in micro-tubular solid oxide electrolysers with yttria-stabilized zirconia (YSZ) electrolyte, Ni-YSZ cermet cathode and strontium(II)-doped lanthanum manganite (LSM) oxygen-evolving anode. At 822 °C, the kinetics of CO 2 reduction were slower (ca. −0.49 A cm −2 at 1.8 V) than H 2 O reduction or co-reduction of CO 2 and H 2 O, which were comparable (ca. −0.83 to −0.77 A cm −2 at 1.8 V). Performances were improved (−0.85 and −1.1 A cm −2 for CO 2 and H 2 O electrolysis, respectively) by substituting the silver current collector with nickel and avoiding blockage of entrances to pores on the inner lumen of micro-tubes induced by silver paste applied previously to decrease contact losses. The change in current collector materials increased ohmic potential losses due to substituting the lower resistance Ag with Ni wire, but decreased electrode polarization losses by 80–93%. For co-electrolysis of CO 2 and H 2 O, isotopically-labelled C 18 O 2 was used to try to distinguish between direct cathodic reduction of CO 2 and its Ni-catalysed chemical reaction with hydrogen from reduction of steam. Unfortunately, oxygen was exchanged between C 18 O 2 and H 2 16 O, enriching oxygen-18 in the steam and substituting oxygen-16 in the carbon dioxide, so the anode off-gas isotopic fractions were meaningless. This occurred even in alumina and YSZ tubes without the micro-tubular reactor, i.e. in the absence of Ni catalyst, though not in quartz tubes

Calculations of kinetic isotope effects in the Hofmann eliminations of substituted (2-phenylethyl)trimethylammonium ions

International Nuclear Information System (INIS)

Lewis, D.E.; Sims, L.B.; Yamataka, H.; McKenna, J.

1980-01-01

Theoretical calculations of kinetic isotope effects (KIE) for the Hofmann elimination of the (2-phenylethyl)trimethylammonium ion (I,Z = H) have been carried out for an extensive series of transition-state models encompassing the Elcb-like region of the E2 mechanistic spectrum. The reaction coordinate employed corresponded to the irreversible fragmentation of the base-H'-C/sub β/-C/sub α/-N system, with proton transfer being the dominant contributor. Structural parameters (bond distances and angles) were related to the independent bond orders n/sub α-N/ and n/sub β-H'/ by empirical and semiempirical relationships. The most probable transition-state structure for the reaction was determined by interpolation of the experimental values for the β-D 2 and 15 N KIE into plots of the trends of the calculated KIE. The nonsolvated models obtained in this manner gave only poor agreement between calculated and experimental secondary deuterium (α-D 2 ) and leaving group deuterium [N(CD 3 )/sub x/(CH 3 )/sub 3-x/, x = 1 to 3) KIE; explicit consideration of differential solvation of the reactant and transition state afforded the most chemically reasonable resolution of these discrepancies. Using solvated models, transition-state structures were also determined for the Hofmann elimination of parasubstituted derivatives of I (Z = OCH 3 , Cl, CF 3 ). These transition states are related by a shift parallel to the central E2 diagogonal of an O'Ferrall-Jencks reaction diagram, as predicted by Thorton, indicating that, in the absence of other factors (differing solvent or base, etc.), the extent to which negative charge is accumulated at Cβ in the transition state is solely a factor of the leaving group. Both independent bond orders (n/sub α-N/ and n/sub β-H'/) exhibit a linear dependence on the sigma value of the substituent, allowing for the first time prediction of transition states

Surface anatomy scanning (SAS) in intracranial tumours: comparison with surgical findings

International Nuclear Information System (INIS)

Sumida, M.; Uozumi, T.; Kiya, K.; Arita, K.; Kurisu, K.; Onda, J.; Satoh, H.; Ikawa, F.; Yukawa, O.; Migita, K.; Hada, H.; Katada, K.

1995-01-01

We evaluated the usefulness of surface anatomy scanning (SAS) in intracranial tumours, comparing it with surgical findings. We examined 31 patients with brain tumours preoperatively. The tumours included 16 meningiomas, 8 gliomas, 4 metastases and 3 others. SAS clearly demonstrated the tumours, allowing them to be distinguished from the structures of the brain surface, including oedema, except in cases of metastasis. SAS clearly demonstrated large cortical veins. SAS is useful for three-dimensional delineation of the brain surface before surgery. (orig.)

Cellular localization of 2-[3H]deoxy-D-glucose from paraffin-embedded brains

International Nuclear Information System (INIS)

Durham, D.; Woolsey, T.A.; Kruger, L.

1981-01-01

Results of experiments in which regional neuronal activity is revealed by a 2-[ 3 H]deoxy-D-glucose ( 3 H-2-DG)-paraffin section-emulsion autoradiography method are described. The trigeminal pathway of freely behaving mice was activated differentially by selective patterns of whisker removal. One hour after injection of concentrated 3 H-2-DG, the animals were perfused systemically with a periodate/lysine/paraformaldehyde mixture the brains were embedded in paraffin, and serial sections were taken and coated with emulsion for autoradiography. Diffusion of the isotope out of the tissue was assessed visually and by liquid scintillation counting. While substantial loss of 3 H isotope into the embedding fluids (about 95%) was found, the scintillation counts and the autoradiograms showed good fixation of the isotope in situ, no evidence of isotope movement into the emulsion, and no gradients of diffusion in the sectioned material. Patterns of regional labeling were similar to those reported from brains prepared by conventional 2-[ 14 C]deoxy-D-glucose ( 14 C-2-DG) autoradiography; Trigeminal structures associated with the intact (stimulated) whiskers were labeled relatively heavily, indicating that label uptake is specific with respect to neuronal activity. In the cortex, the patterns of label corresponded directly and precisely to those barrels known to receive inputs from the intact whiskers. Distribution of silver grains in the cortex and in the brainstem was correlated directly with neuronal profiles. Clearly, this approach offers considerable technical advantages, in particular, the ease with which the histological material is prepared. The resolution of the autoradiograms and the quality of the histology are excellent

Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

International Nuclear Information System (INIS)

Chiba, H.; Sakai, H.

1985-01-01

Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300 deg C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H 2 SO 4 0 and H 2 O at low pH, and between HSO 4 - and H 2 O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10 9 years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates. (author)

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

Science.gov (United States)

Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

2017-12-01

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

First report of sasX-positive methicillin-resistant Staphylococcus aureus in Japan.

Science.gov (United States)

Nakaminami, Hidemasa; Ito, Teruyo; Han, Xiao; Ito, Ayumu; Matsuo, Miki; Uehara, Yuki; Baba, Tadashi; Hiramatsu, Keiichi; Noguchi, Norihisa

2017-09-01

SasX is a known virulence factor of Staphylococcus aureus involved in colonisation and immune evasion of the bacterium. The sasX gene, which is located on the ϕSPβ prophage, is frequently found in the sequence type (ST) 239 S. aureus lineage, which is the predominant healthcare-associated clone in Asian countries. In Japan, ST239 clones have rarely been identified, and sasX-positive strains have not been reported to date. Here, we report the first identification of 18 sasX-positive methicillin-resistant S. aureus (MRSA) strains in Japanese hospitals between 2009 and 2011. All sasX-positive isolates belonged to an ST239-staphylococcal cassette chromosome mec type III (ST239-III) lineage. However, we were unable to identify additional sasX-positive MRSA strains from 2012 to 2016, indicating that the small epidemic of sasX-positive isolates observed in this study was temporary. The sequence surrounding sasX in the strain TOHH628 lacked 51 genes that encode phage packaging and structural proteins, and no bacteriophage was induced by mitomycin C. Additionally, in the TOHH628 strain, the region (64.6 kb) containing sasX showed high identity to the ϕSPβ-like element (71.3 kb) of the Taiwanese MRSA strain Z172. The data strongly suggest that the present sasX-positive isolates found in Japanese hospitals were transmitted incidentally from other countries. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Development and validation of a smartphone addiction scale (SAS.

Directory of Open Access Journals (Sweden)

Min Kwon

Full Text Available OBJECTIVE: The aim of this study was to develop a self-diagnostic scale that could distinguish smartphone addicts based on the Korean self-diagnostic program for Internet addiction (K-scale and the smartphone's own features. In addition, the reliability and validity of the smartphone addiction scale (SAS was demonstrated. METHODS: A total of 197 participants were selected from Nov. 2011 to Jan. 2012 to accomplish a set of questionnaires, including SAS, K-scale, modified Kimberly Young Internet addiction test (Y-scale, visual analogue scale (VAS, and substance dependence and abuse diagnosis of DSM-IV. There were 64 males and 133 females, with ages ranging from 18 to 53 years (M = 26.06; SD = 5.96. Factor analysis, internal-consistency test, t-test, ANOVA, and correlation analysis were conducted to verify the reliability and validity of SAS. RESULTS: Based on the factor analysis results, the subscale "disturbance of reality testing" was removed, and six factors were left. The internal consistency and concurrent validity of SAS were verified (Cronbach's alpha = 0.967. SAS and its subscales were significantly correlated with K-scale and Y-scale. The VAS of each factor also showed a significant correlation with each subscale. In addition, differences were found in the job (p<0.05, education (p<0.05, and self-reported smartphone addiction scores (p<0.001 in SAS. CONCLUSIONS: This study developed the first scale of the smartphone addiction aspect of the diagnostic manual. This scale was proven to be relatively reliable and valid.

Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects

International Nuclear Information System (INIS)

Engdahl, K.A.; Bivehed, H.; Ahlberg, P.; Saunders, W.H. Jr.

1983-01-01

Primary and secondary deuterium isotope effects have been measured by polarimetry, and primary isotope effects have been calculated for the classical bifunctional catalysis: 2-pyridinone-catalyzed mutarotation of 2,3,4,6-tetra-O-methyl-α-D-glucopyranose (α-TMG) in benzene. From the positively curved plot of the specific rate of epimerization vs. the mole fraction of 2 H in the ''pool'' of OH and NH hydrogens, the isotope effects k/sub HH//k/sub DD/ = 3.66 +/- 0.09, k/sub HH//k/sub DH/ = 1.5, and k/sub HH//k/sub HD/ = 2.4 have been calculated. A secondary isotope effect of 1.14 +/- 0.02 has been measured by using α-TMG and (1- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(l- 2 H)-α-TMG], the synthesis of which is described in detail, together with those for (N- 2 H)-2-pyridinone and (1-O- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(1-O- 2 H)-α-TMG]. The rate data obtained have also been analyzed by fractionation theory, yielding approximately equal fractionation factors (0.5). The interpretation of the results has been assisted by calculations of the primary deuterium isotope effects using the BEBOVIB IV program. Two models involving small and considerable coupling, respectively, of the transferring protons to heavy-atom motion have been considered. In the favored structure for the transition state of the rate-limiting step, two protons are in transit, and their motion is governed either by a potential with a barrier or by one without. Their motion is considerably coupled to the heavy-atom motion (i.e., the breakage of the ring C-O bond), and tunnel corrections to the isotope effects are found to be negligible

Hotelli Radisson SAS mantra : jah, ma saan! / Kai Vare

Index Scriptorium Estoniae

Vare, Kai, 1968-

2004-01-01

Radisson SAS hotell Tallinnas on kliendirahulolu-uuringute järgi keti hotellide seas esimeste hulgas. Hotelli direktor Kaido Ojaperv ja müügijuht Ann-Kai Tõrs Radisson SAS-i standarditest, kliendi sajaprotsendilise rahulolu tagamise põhimõtetest, personali valikust, koolitusest. Kommenteerib Sandra Dimitrovich

SAS validation and analysis of in-pile TUCOP experiments

International Nuclear Information System (INIS)

Morman, J.A.; Tentner, A.M.; Dever, D.J.

1985-01-01

The validation of the SAS4A accident analysis code centers on its capability to calculate the wide range of tests performed in the TREAT (Transient Reactor Test Facility) in-pile experiments program. This paper presents the SAS4A analysis of a simulated TUCOP (Transient-Under-Cooled-Over-Power) experiment using seven full-length PFR mixed oxide fuel pins in a flowing sodium loop. Calculations agree well with measured thermal-hydraulic, pin failure time and post-failure fuel motion data. The extent of the agreement confirms the validity of the models used in the SAS4A code to describe TUCOP accidents

Isotope effects and their implications for the covalent binding of inhaled [3H]- and [14C]formaldehyde in the rat nasal mucosa

International Nuclear Information System (INIS)

Heck Hd'; Casanova, M.

1987-01-01

DNA-protein crosslinks were formed in the nasal respiratory mucosa of Fischer-344 rats exposed for 3 hr to selected concentrations of [ 3 H]- and [ 14 C]formaldehyde ( 3 HCHO and H 14 CHO). In rats depleted of glutathione (GSH) and exposed to 10 ppm of 3 HCHO and H 14 CHO, the 3 H/ 14 C ratio of the fraction of the DNA that was crosslinked to proteins was significantly (39 +/- 6%) higher than that of the inhaled gas. This suggests an isotope effect, either on the formation of DNA-protein crosslinks by labeled HCHO or on the oxidation of labeled HCHO catalyzed by formaldehyde (FDH) or aldehyde dehydrogenase (AldDH). The possibility of an isotope effect on the formation of crosslinks was investigated using rat hepatic nuclei incubated with [ 3 H]- and [ 14 C]formaldehyde (0.1 mM, 37 degrees C). A small (3.4 +/- 0.9%) isotope effect was detected on this reaction, which slightly favored 3 HCHO over H 14 CHO in binding to DNA. The magnitude of this isotope effect cannot account for the high isotope ratio observed in the crosslinked DNA in vivo. The possibility of an isotope effect on the oxidation of 3 HCHO and H 14 CHO catalyzed by FDH was investigated using homogenates of the rat nasal mucosa incubated with [ 3 H]- and [ 14 C]formaldehyde at total formaldehyde concentrations ranging from 0.1 to 11 microM, NAD+ (1 mM), GSH (15 mM), and pyrazole (1 mM). The experiments showed that 3 HCHO is oxidized significantly more slowly than H 14 CHO under these conditions (Vmax/Km (H 14 CHO) divided by Vmax/Km ( 3 HCHO) = 1.82 +/- 0.11). A similar isotope effect was observed in the absence of GSH, presumably due to the oxidation of 3 HCHO and H 14 CHO catalyzed by AldDH

Isotopically labelled pyrimidines and purines

International Nuclear Information System (INIS)

Balaban, A.T.; Bally, I.

1987-01-01

Among the three diazines, pyrimidine is by far the most important one because its derivatives uracil, thymine and cytosine are constituents of the ubiquitous deoxynucleic acids (DNA) and ribonucleic acids (RNA). Other derivatives of pyrimidine without condensed rings include barbiturates, alloxan, orotic acid and thiamine or vitamin B 1 . From the polycyclic derivatives of pyrimidine such as pteridine, alloxazine, and purine, the latter, through its derivatives adenine and guanine complete the list of bases which occur in DNA and RNA: in addition, other purine derivatives such as hypoxanthine, xanthine, theobromine, theophylline, caffeine and uric acid are important natural products with biological activity. The paper presents methods for preparing isotopically labeled pyrimidines as well as purine derivatives. For convenience, the authors describe separately carbon-labeled with radioisotopes 11 C (T 1/2 = 20.3 min) and 14 C (T 1/2 = 5736 years) or the stable isotope 13 C (natural abundance 1.1%) and then hydrogen-labeled systems with the radioisotope 3 H ≡ T (T 1/2 = 12.346 years) or with the stable isotope 2 H ≡ D (natural abundance 0.015%). We do not separate stable from radioactive isotopes because the synthetic methods are identical for the same element; however, the introduction of hydrogen isotopes into organic molecules is often performed by reactions such as isotope exchange which cannot take place in the case of carbon isotopes

Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2

Science.gov (United States)

Rhee, Young Min; Kim, Myung Soo

1998-10-01

The deuterium isotope effect on the product energy partitioning in the title reaction was investigated both experimentally and theoretically. The measured kinetic energy release (KER) showed a significant dependence on the position of deuteration. A reliable potential energy surface of the reaction was constructed from ab initio results using the recently developed interpolation algorithm. The classical trajectory calculation on this surface well reproduced the experimental finding. Close inspection of the potential energy surface revealed that the isotope effect on KER and the product rotations arose from the alteration of the symmetry of the reaction path near the transition state induced by the mass change upon isotopic substitution. The product vibrations were found to be affected by the change in the coupling constants which also arose from the mass-dependent change in the reaction path. Possibility of the quantum mechanical tunneling was also considered. Tunneling-corrected classical trajectory results were in excellent agreement with the experimental ones, indicating that the reaction proceeds via barrier penetration below the threshold.

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

Science.gov (United States)

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

2013-06-01

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

Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies