WorldWideScience

Sample records for isotope effect evidence

  1. Is there a stable isotope evidence for the CO 2 fertiliser effect

    Indian Academy of Sciences (India)

    Stable carbon and hydrogen isotope ratios of cellulose extracted from annual growth rings (covering the time period 1980-1993) in an oak tree from Kalamazoo, SW Michigan provide a basis to investigate at a physiological level how the fertilization effect may operate. The carbon isotope ratios show that the intercellular ...

  2. Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

    International Nuclear Information System (INIS)

    Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert

    2013-01-01

    Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

  3. Isotope effects on chemical equilibria

    International Nuclear Information System (INIS)

    Golding, P.D.

    1974-01-01

    The thermodynamic equilibrium constants of three deuterated substituted acetic acids are reported. The calculation of secondary isotope effects of the second kind for the three isotopic acid pairs has been accomplished by the appropriate comparison of thermodynamic equilibrium constants, and by the comparison of isotopic slopes. The effect of substituent variation on the isotope effects reported here disqualifies the simple inductive model as a legitimate description of secondary isotope effects of the second kind. The correlation of diminishing isotope effect per deuterium atom with increasing acidity is also invalidated by the present results. The syntheses of 9-thia-9,10-dihydrophenanthrene-9-oxide and thioxanthene-10-oxide are described. These compounds have been partially deuterated at their respective methylene positions. Spectral evidence indicates stereoselectivity of the methylene protons in the exchange reactions of both compounds. (author)

  4. Evidence of a kinetic isotope effect in nanoaluminum and water combustion.

    Science.gov (United States)

    Tappan, Bryce C; Dirmyer, Matthew R; Risha, Grant A

    2014-08-25

    The normally innocuous combination of aluminum and water becomes violently reactive on the nanoscale. Research in the field of the combustion of nanoparticulate aluminum has important implications in the design of molecular aluminum clusters, hydrogen storage systems, as well as energetic formulations which could use extraterrestrial water for space propulsion. However, the mechanism that controls the reaction speed is poorly understood. While current models for micron-sized aluminum water combustion reactions place heavy emphasis on diffusional limitations, as reaction scales become commensurate with diffusion lengths (approaching the nanoscale) reaction rates have long been suspected to depend on chemical kinetics, but have never been definitely measured. The combustion analysis of nanoparticulate aluminum with H2O or D2O is presented. Different reaction rates resulting from the kinetic isotope effect are observed. The current study presents the first-ever observed kinetic isotope effect in a metal combustion reaction and verifies that chemical reaction kinetics play a major role in determining the global burning rate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Isotopic evidence of the effects of herbivory and landscape position on plant nitrogen sources in a riparian ecosystem.

    Science.gov (United States)

    Menezes, Rômulo S C

    2009-03-01

    This study used (15)N natural abundance techniques to investigate whether elk herbivory affects the capability of willow (Salix spp.) and reed-grass (Carex spp.) to access N from groundwater in upper and lower landscape positions within riparian areas of the Rocky Mountain National Park. For this, delta(15)N values of plant, soil, rainfall and groundwater samples were measured within a replicated field experiment. Despite the relatively high variability in the (15)N data, it provided evidence of the effects of grazing and lanscape position on plant N sources. Carex seemed to acquire less groundwater N in upper landscape positions compared to Salix, maybe due to the deeper willow rooting system. However, grazed willows in upper landscape positions seemed to acquire less groundwater N as compared to willows protected from herbivory. These findings were in accordance with other isotopic and non-isotopic studies conducted in the same experimental site.

  6. Secondary hydrogen isotope effects

    International Nuclear Information System (INIS)

    Melander, L.; Sonders, U.

    1983-01-01

    Secondary isotope effects can be produced by isotopes of elements heavier than hydrogen, but secondary isotope effects of hydrogen are of greater interest, because they are larger and can be measured easier. Such aspects of the problem as solvolytic reactions (in the case of α-position and β-position in organic compounds), reactions of compounds with deuterium remoted from reaction centre, with deuterium in nonsaturated compounds, participation of neighbouring groups in the reaction, are considered. Besides, steric isotope effects and inductive isotope effects are considered

  7. New evidence for symmetry dependent isotope effects: O+CO reaction

    International Nuclear Information System (INIS)

    Bhattacharya, S.K.; Thiemens, M.H.

    1989-01-01

    The isotopic fractionation associated with the O + CO reaction has been studied using oxygen atoms produced by room temmperature O 2 photolysis at two different wavelengths, 185 and 130 nm. A large mass-independent isotopic fractionation is observed in the product CO 2 , extending the range of this type of reaction beyond O + O 2 and SF 5 + SF 5 . Kinetic evaluation of the data restricts the source of the mass-independent fractionation mechanism to the O + CO recombination step rather than O 2 photolysis, secondary ozone formation, or O 2 photodissociation. At least one, and most likely two other fractionation processes appear to occur in the experiments, and interpretation of the isotopic results is tentative at present. Based on the relevant reaction rates and the value for the reduced partition function for isotopic exchange between O and CO, it is suggested that this process may occur prior to the δ 17 O≅δ 18 O recombination process. Secondary CO 2 photolysis may superimpose an additional fractionation. The experimental data are also examined in the context of a model based upon energy randomization rates versus the lifetime of the activated complex. (orig.)

  8. Hf isotope evidence for effective impact melt homogenisation at the Sudbury impact crater, Ontario, Canada

    Science.gov (United States)

    Kenny, Gavin G.; Petrus, Joseph A.; Whitehouse, Martin J.; Daly, J. Stephen; Kamber, Balz S.

    2017-10-01

    We report on the first zircon hafnium-oxygen isotope and trace element study of a transect through one of the largest terrestrial impact melt sheets. The differentiated melt sheet at the 1.85 Ga, originally ca. 200 km in diameter Sudbury impact crater, Ontario, Canada, yields a tight range of uniform zircon Hf isotope compositions (εHf(1850) of ca. -9 to -12). This is consistent with its well-established crustal origin and indicates differentiation from a single melt that was initially efficiently homogenised. We propose that the heterogeneity in other isotopic systems, such as Pb, in early-emplaced impact melt at Sudbury is associated with volatility-related depletion during the impact cratering process. This depletion leaves the isotopic systems of more volatile elements more susceptible to contamination during post-impact assimilation of country rock, whereas the systems of more refractory elements preserve initial homogeneities. Zircon oxygen isotope compositions in the melt sheet are also restricted in range relative to those in the impacted target rocks. However, they display a marked offset approximately one-third up the melt sheet stratigraphy that is interpreted to be a result of post-impact assimilation of 18O-enirched rocks into the base of the cooling impact melt. Given that impact cratering was a more dominant process in the early history of the inner Solar System than it is today, and the possibility that impact melt sheets were sources of ex situ Hadean zircon grains, these findings may have significance for the interpretation of the early zircon Hf record. We speculate that apparent εHf-time arrays observed in the oldest terrestrial and lunar zircon datasets may be related to impact melting homogenising previously more diverse crust. We also show that spatially restricted partial melting of rocks buried beneath the superheated impact melt at Sudbury provided a zircon crystallising environment distinct to the impact melt sheet itself.

  9. 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

  10. Isotopic effect giant resonances

    International Nuclear Information System (INIS)

    Buenerd, M.; Lebrun, D.; Martin, P.; Perrin, G.; Saintignon, P. de; Chauvin, J.; Duhamel, G.

    1981-10-01

    The systematics of the excitation energy of the giant dipole, monopole, and quadrupole resonances are shown to exhibit an isotopic effect. For a given element, the excitation energy of the transition decreases faster with the increasing neutron number than the empirical laws fitting the overall data. This effect is discussed in terms of the available models

  11. Isotope effects on nuclear shielding

    International Nuclear Information System (INIS)

    Hansen, P.E.

    1983-01-01

    This review concentrates upon empirical trends and practical uses of mostly secondary isotope effects, both of the intrinsic and equilibrium types. The text and the tables are arranged in the following fashion. The most 'popular' isotope effect is treated first, deuterium isotope effects on 13 C nuclear shielding, followed by deuterium on 1 H nuclear shieldings, etc. Focus is thus on the isotopes producing the effect rather than on the nuclei suffering the effect. After a brief treatment of each type of isotope effect, general trends are dealt with. Basic trends of intrinsic isotope effects such as additivity, solvent effects, temperature effects, steric effects, substituent effects and hyperconjugation are discussed. Uses of isotope effects for assignment purposes, in stereochemical studies, in hydrogen bonding and in isotopic tracer studies are dealt with. Kinetic studies, especially of phosphates, are frequently performed by utilizing isotope effects. In addition, equilibrium isotope effects are treated in great detail as these are felt to be new and very important and may lead to new uses of isotope effects. Techniques used to obtain isotope effects are briefly surveyed at the end of the chapter. (author)

  12. Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular 12C/13C Kinetic Isotope Effects

    Science.gov (United States)

    Gonzalez-James, Ollie M.; Zhang, Xue; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Singleton, Daniel A.

    2010-01-01

    The intramolecular 13C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 °C to 1.163 at −100 °C. Semi-classical calculations employing canonical variational transition state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening. PMID:20722415

  13. Isotopic evidence for oxygenated Mesoarchaean shallow oceans

    Science.gov (United States)

    Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny

    2018-02-01

    Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

  14. Mass-independent isotope effects.

    Science.gov (United States)

    Buchachenko, Anatoly L

    2013-02-28

    Three fundamental properties of atomic nuclei-mass, spin (and related magnetic moment), and volume-are the source of isotope effects. The mostly deserved and popular, with almost hundred-year history, is the mass-dependent isotope effect. The first mass-independent isotope effect which chemically discriminates isotopes by their nuclear spins and nuclear magnetic moments rather than by their masses was detected in 1976. It was named as the magnetic isotope effect because it is controlled by magnetic interaction, i.e., electron-nuclear hyperfine coupling in the paramagnetic species, the reaction intermediates. The effect follows from the universal physical property of chemical reactions to conserve angular momentum (spin) of electrons and nuclei. It is now detected for oxygen, silicon, sulfur, germanium, tin, mercury, magnesium, calcium, zinc, and uranium in a great variety of chemical and biochemical reactions including those of medical and ecological importance. Another mass-independent isotope effect was detected in 1983 as a deviation of isotopic distribution in reaction products from that which would be expected from the mass-dependent isotope effect. On the physical basis, it is in fact a mass-dependent effect, but it surprisingly results in isotope fractionation which is incompatible with that predicted by traditional mass-dependent effects. It is supposed to be a function of dynamic parameters of reaction and energy relaxation in excited states of products. The third, nuclear volume mass-independent isotope effect is detected in the high-resolution atomic and molecular spectra and in the extraction processes, but there are no unambiguous indications of its importance as an isotope fractionation factor in chemical reactions.

  15. Isotope effects in photochemical rearrangements

    International Nuclear Information System (INIS)

    Sommer, F.

    1983-01-01

    Taking anthracene resp. 9-deuteroanthracene as the initial substance, different substitution products have been prepared. The products originating by direct photolysis have been characterized and their structure has been determined. By comparing the measured kinetic isotope effect and the quantum yield of the nondeuterated and the monodeuterated fluorenes formed it could been demonstrated that the isotope effect mainly is due to the reaction rates and the influence of the deuterium substitution upon the radiationless desactivation against that is small. (HBR) [de

  16. Isotope effects in gas-phase chemistry

    International Nuclear Information System (INIS)

    Various aspects of isotope effects in chemical reactions and photochemical reactions are presented. Most studies consider kinetic isotope effects with emphasis on hydrogen, deuterium, and muonium containing molecules and atoms. Theoretical origins of kinetic isotope effects are considered in several papers. A few of the latter papers consider atmospheric chemistry with respect to isotope effects

  17. Important Crustal Growth in the Phanerozoic: Isotopic Evidence of ...

    Indian Academy of Sciences (India)

    Important Crustal Growth in the Phanerozoic: Isotopic Evidence of Granitoids from East-Central Asia ... based on Nd isotopic data, the mass of new crust formed in the East-Central Asian Orogenic Belt (ECAOB), eastern part of the Altaid Tectonic Collage, appears to be much greater than the above terranes combined.

  18. The effectiveness of using carbonate isotope measurements of body tissues to infer diet in human evolution: Evidence from wild western chimpanzees (Pan troglodytes verus).

    Science.gov (United States)

    Fahy, Geraldine E; Boesch, Christophe; Hublin, Jean-Jacques; Richards, Michael P

    2015-11-01

    Changes in diet throughout hominin evolution have been linked with important evolutionary changes. Stable carbon isotope analysis of inorganic apatite carbonate is the main isotopic method used to reconstruct fossil hominin diets; to test its effectiveness as a paleodietary indicator we present bone and enamel carbonate carbon isotope data from a well-studied population of modern wild western chimpanzees (Pan troglodytes verus) of known sex and age from Taï, Cote d'Ivoire. We found a significant effect of age class on bone carbonate values, with adult chimpanzees being more (13)C- and (18)O-depleted compared to juveniles. Further, to investigate habitat effects, we compared our data to existing apatite data on eastern chimpanzees (P. troglodytes schweinfurthii) and found that the Taï chimpanzees are significantly more depleted in enamel δ(13)Cap and δ(18)Oap compared to their eastern counterparts. Our data are the first to present a range of tissue-specific isotope data from the same group of wild western chimpanzees and, as such, add new data to the growing number of modern non-human primate comparative isotope datasets providing valuable information for the interpretation of diet throughout hominin evolution. By comparing our data to published isotope data on fossil hominins we found that our modern chimpanzee bone and enamel data support hypotheses that the trend towards increased consumption of C4 foods after 4 Ma (millions of years ago) is unique to hominins. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 1. Variation of kinetic isotope ... An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence ...

  20. Isotope effect and isotope separation. A chemist's view

    International Nuclear Information System (INIS)

    Ishida, Takanobu

    2002-01-01

    What causes the isotope effects (IE)? This presentation will be centered around the equilibrium isotope effects due to the differences in the nuclear masses. The occurrence of the equilibrium constant, K, of isotope exchange reactions which differ from the values predicted by the classical theory of statistical mechanics, K cl , is explored. The non-classical K corresponds to the unit-stage separation factor, α, that is different from unity and forms a basis of an isotope separation process involving the chemical exchange reaction. Here, the word 'chemical exchange' includes not only the isotope exchange chemical reactions between two or more chemical species but also the isotope exchanges involving the equilibria between liquid and vapor phases and liquid-gas, liquid solution-gas, liquid-liquid, and solid-liquid phases. In Section I, origins of the isotope effect phenomena will be explored and, in the process, various quantities used in discussions of isotope effect that have often caused confusions will be unambiguously defined. This Section will also correlate equilibrium constant with separation factor. In Section II, various forms of temperature-dependence of IE and separation factor will be discussed. (author)

  1. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    The isotopic fractionation associated with photodissociation of N2O, OCS and CO2, at different altitudes in Earth’s atmosphere, is investigated theoretically using constructed quantum mechanical models of the dissociation processes (i.e. potential energy surfaces and relevant coupling elements......’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...... in heavy carbon. The sulfur fractionation is weak and photolysis of OCS in the stratosphere produces only a small and mass dependent enrichment of heavy sulfur isotopes in the remaining OCS. Sulfur fractionation from the two remaining chemical sinks (oxidation by O(3P) and OH, respectively) is weak...

  2. Isotope hydrological evidence of geomorphological changes in northeastern Hungary

    International Nuclear Information System (INIS)

    Hertelendi, E.; Marton, L.; Miko, L.

    1992-01-01

    An isotope hydrological survey of groundwaters in the northeastern part of Hungary has shown a distribution of stable isotopic composition that cannot be explained by climatic changes alone. Detailed geomorphological studies have pointed out that during the Upper Pleniglacial and Late Glacial, the morphology of the territory, and consequently its catchment area, underwent considerable changes. Data gathered by the authors are consistent with the geomorphological results. The distribution of the isotopic composition data of groundwater provides evidence of both climatic changes and tectonic movements in the area. (author). 8 refs, 7 figs

  3. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    ’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...

  4. Isotopic evidence of Middle Proterozoic magmatism from Bombay ...

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    Isotopic evidence of Middle Proterozoic magmatism from. Bombay High Field: Implications to crustal evolution of western offshore of India. S S Rathore1,∗, A R Vijan2, M P Singh2, B N Prabhu3 and Anand Sahu1. 1Forward Base Office, Assam & Assam Arakan Basin-Tripura, ONGC, Agartala 799 014, India.

  5. Isotopically sensitive branching and its effect on the observed intramolecular isotope effects in cytochrome P-450 catalyzed reactions: a new method for the estimation of intrinsic isotope effects

    International Nuclear Information System (INIS)

    Jones, J.P.; Korzekwa, K.R.; Rettie, A.E.; Trager, W.F.

    1986-01-01

    Two selectively deuterated n-octanes (octane-1- 2 H 3 and octane-1,2,3- 2 H 7 ) were synthesized and subjected to hydroxylation by phenobarbital-induced rat liver microsomes and purified cytochrome P-450b. The results of these experiments provide evidence which clarifies the interplay between a branched reaction pathway and the equilibration of an enzyme-substrate complex, in determining the magnitude of an observed isotope effect. An equation is derived that allows limits to placed on the intrinsic isotope effect. The equation is based on the observed isotope effect and the regioselectivity of a branch reaction pathway, catalyzed by an enzyme that forms two products via a single enzyme-substrate complex. The intrinsic isotope effect for the formation of 1-octanol was determined by this equation to lie between 9.5 and 9.8

  6. Zinc isotopic evidence for the origin of the Moon.

    Science.gov (United States)

    Paniello, Randal C; Day, James M D; Moynier, Frédéric

    2012-10-18

    Volatile elements have a fundamental role in the evolution of planets. But how budgets of volatiles were set in planets, and the nature and extent of volatile-depletion of planetary bodies during the earliest stages of Solar System formation remain poorly understood. The Moon is considered to be volatile-depleted and so it has been predicted that volatile loss should have fractionated stable isotopes of moderately volatile elements. One such element, zinc, exhibits strong isotopic fractionation during volatilization in planetary rocks, but is hardly fractionated during terrestrial igneous processes, making it a powerful tracer of the volatile histories of planets. Here we present high-precision zinc isotopic and abundance data which show that lunar magmatic rocks are enriched in the heavy isotopes of zinc and have lower zinc concentrations than terrestrial or Martian igneous rocks. Conversely, Earth and Mars have broadly chondritic zinc isotopic compositions. We show that these variations represent large-scale evaporation of zinc, most probably in the aftermath of the Moon-forming event, rather than small-scale evaporation processes during volcanism. Our results therefore represent evidence for volatile depletion of the Moon through evaporation, and are consistent with a giant impact origin for the Earth and Moon.

  7. A new scheme to calculate isotope effects.

    Science.gov (United States)

    Swiderek, Katarzyna; Dybala-Defratyka, Agnieszka; Rohr, Daniel R

    2011-09-01

    We present a new scheme to calculate isotope effects. Only selected frequencies at the target level of theory are calculated. The frequencies are selected by an analysis of the Hessian from a lower level of theory. We obtain accurate isotope effects without calculating the full Hessian at the target level of theory. The calculated frequencies are very accurate. The scheme converges to the correct isotope effect.

  8. Reaction kinetics: mechanisms and isotope effects

    International Nuclear Information System (INIS)

    Jones, J.R.

    1977-01-01

    This chapter emphasized how the isotope effects are obtained, and the factors that govern their magnitude. Most of the discussion concerned hydrogen isotope effects. Of the other isotopes much work has been done on carbon. Less extensive studies were reported using the isotopes of chlorine ( 35 Cl, 37 Cl), sulfur ( 32 S, 34 S), nitrogen ( 14 N, 15 N), and oxygen ( 16 O, 17 O). The customary way of altering the symmetry of the transition state is to vary the strength of the base B. Very large primary kinetic hydrogen isotope effects have also been observed for nitrocompounds. Some hydrogen alien reactions which may also be characterized by small solvation changes exhibit extremely large K/sup H//K/sup D/ values. Recently the main application of secondary hydrogen isotope effects has been in the study of the ability of neighboring groups to alter the energetics of organic reactions. 1 figure, 5 tables

  9. Medium Effects in Reactions with Rare Isotopes

    International Nuclear Information System (INIS)

    Bertulani, C A; Karakoç, M

    2012-01-01

    We discuss medium effects in knockout reactions with rare isotopes of weakly-bound nuclei at intermediate energies. We show that the poorly known corrections may lead to sizable modifications of knockout cross sections and momentum dsitributions.

  10. Isotopic and Chemical Evidence for Primitive Aqueous Alteration in the Tagish Lake Meteorite

    Science.gov (United States)

    Sakuma, Keisuke; Hidaka, Hiroshi; Yoneda, Shigekazu

    2018-01-01

    Aqueous alteration is one of the primitive activities that occurred on meteorite parent bodies in the early solar system. The Tagish Lake meteorite is known to show an intense parent body aqueous alteration signature. In this study, quantitative analyses of the alkaline elements and isotopic analyses of Sr and Ba from acid leachates of TL (C2-ungrouped) were performed to investigate effects of aqueous alteration. The main purpose of this study is to search for isotopic evidence of extinct 135Cs from the Ba isotopic analyses in the chemical separates from the Tagish Lake meteorite. Barium isotopic data from the leachates show variable 135Ba isotopic anomalies (ε = ‑2.6 ∼ +3.6) which correlatewith 137Ba and 138Ba suggesting a heterogeneous distribution of s- and r-rich nucleosynthetic components in the early solar system. The 87Rb–87Sr and 135Cs–135Ba decay systems on TL in this study do not provide any chronological information. The disturbance of the TL chronometers is likely a reflection of the selective dissolution of Cs and Rb given the relatively higher mobility of Cs and Rb compared to Ba and Sr, respectively, during fluid mineral interactions.

  11. Bibliography on vapour pressure isotope effects

    International Nuclear Information System (INIS)

    Illy, H.; Jancso, G.

    1976-03-01

    The bibliography of research on vapour pressure isotope effects from 1919 to December 1975 is presented in chronological order. Within each year the references are listed alphabetically according to the name of the first author of each work. The bibliography is followed by a Compound Index containing the names o compounds, but the type of isotopic substituation is not shown. The Author Index includes all authors of the papers. (Sz.N.Z.)

  12. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Proton transfer; promoter modes; kinetic isotope effect. 1. Introduction. Kinetic isotope effect (KIE) is the dependence of the rate constant on the mass of the isotope of the atom in a chemical reaction. The primary kinetic isotope effect is the KIE when the bonds connecting that atom to the rest of the molecular frame are broken ...

  13. Isotopic effect in high temperature superconductors

    International Nuclear Information System (INIS)

    Ohno, Takashi

    2000-01-01

    It is well-known that it essentially contributed to construct the BCB theory that a mechanism on formation of the Cooper pairs was dependent upon a lattice oscillation to change a critical temperature, T(sub c) of a superconductor with isotopic displacement. In this paper, here was, at first, described on an isotopic index actually measured to high temperature superconductors, and was introduced on a study on selective displacement of oxygen position. And then, a detailed measurement of 63-Cu(2) nuclear quadrupole resonance (NQR) at a plane position of YBa2Cu4O8 (Y1248) displaced with 18-O and 16-O, discussion of the isotopic effect on a base of 63-Cu(2) nuclear spin-lattice relaxation ratio, and consideration on the isotopic index according to the isotopic effect were described. As a result of the considerations, it could be concluded that the isotopic effect in a high temperature superconductor proved that antiferromagnetic spin fluctuation was an origin of Cooper pairs cohesive strength. (G.K.)

  14. Effects of mining activities on evolution of water quality of karst waters in Midwestern Guizhou, China: evidences from hydrochemistry and isotopic composition.

    Science.gov (United States)

    Li, Xuexian; Wu, Pan; Han, Zhiwei; Zha, Xuefang; Ye, Huijun; Qin, Yingji

    2018-01-01

    Zhijin coal-mining district, located in Midwestern Guizhou Province, has been extensively exploited for several decades. The discharge of acid mine drainage (AMD) has constituted a serious threat to local water environmental quality, which greatly affected the normal use of local people. The Permian limestone aquifer is the essential potable water supply for local people, which covered under the widely distributed coal seams. To investigate the origin of the water, the evolutionary processes, and the sources of dissolved sulfate in the karst waters, the mine water, surface water, and groundwater near the coal mines were sampled for stable isotopes (H, O, and S) and conventional hydrochemical analysis. The results of hydrochemistry and isotopic composition indicate that the regional surface water and partial karst groundwater are obviously affected by coal-mining activities, which is mainly manifested in the increase of water solute concentration and the change of hydrochemical types. The isotopic composition of δ 2 H H2O and δ 18 O H2O indicates that the major recharge source of surface water and the groundwater is atmospheric precipitation and that it is influenced obviously by evaporation in the recharge process. The surface water is mainly controlled by the oxidation of pyrite, as well as the dissolution of carbonate rocks, whereas that of natural karst waters is influenced by the dissolution of carbonate rocks. The resulting δ 34 S SO4 values suggest that the dissolved sulfate source in the surface water is mainly pyrite oxidation but atmospheric precipitation for the karst groundwater. Given the similar chemistry and isotopic composition between surface water and partial groundwater, it is reasonable to assume that most of the dissolved sulfate source in part of the groundwater was derived through the oxidation of pyrite in the coal. Furthermore, the contamination of the surface water and partial groundwater from the coal seam has occurred distinctly in the

  15. Modeling nuclear volume isotope effects in crystals

    Science.gov (United States)

    Schauble, Edwin A.

    2013-01-01

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac–Hartree–Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor–crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from 119Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium

  16. Stable isotope 'vital effects' in coccolith calcite

    NARCIS (Netherlands)

    Ziveri, P.; Stoll, H.; Probert, I.; Klaas, C.; Geisen, M.; Ganssen, G.M.; Young, J.

    2003-01-01

    Uncertainties about the origin of the many disequilibrium or 'vital effects' in a variety of calcifying organisms, and whether these effects are constant or variable, have hampered paleoceanographic application of carbon and oxygen isotopic ratios. Unraveling the source of these effects will improve

  17. Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

    Science.gov (United States)

    Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

    2011-12-01

    Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

  18. Anomalous oxygen isotopic charge state distribution in ECRIS : New evidence

    NARCIS (Netherlands)

    Drentje, AG; Girard, A; Hitz, D; Melin, G

    The highly performing Electron Cyclotron Resonance Ion Source CAPRICE in Grenoble was operated with a mixture of three oxygen isotopes. The summed currents per charge state show a distribution almost identical to that of natural oxygen. However, the distributions per isotope are distinctly and

  19. Isotopic evidence for multiple contributions to felsic magma chambers

    DEFF Research Database (Denmark)

    Waight, Tod Earle; Wiebe, R.A.; Krogstad, E.J.

    2007-01-01

    with identical isotopic compositions to more mafic dikes suggest that closed system fractionation may be occurring in deeper level chambers prior to injection to shallower levels. The granitic portion of the pluton has the highest Nd isotopic composition (eNd=+3.0) of plutons in the region whereas the mafic...

  20. Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

    Science.gov (United States)

    Fitzpatrick, Paul F.

    2014-01-01

    Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

  1. Stereochemistry and kinetic deuterium isotope effects in the thermal 1,3-sigmatropic rearrangement of (-)-(R,R)-trans-2-methyl-1-(1-tert-butylvinyl)cyclopropane: evidence for a biradical intermediate

    International Nuclear Information System (INIS)

    Gajewski, J.J.; Warner, J.M.

    1984-01-01

    The mechanism of the thermally induced, first order 1,3-chemical shift in cyclopropanes has not been clearly defined. In an effort to resolve the mechanism of the 1,3-shift, (-)-(R,R)-trans-2-methyl-1-(1-tert-butylvinyl) cyclopropane and its 1-(2,2-dideuterio-1-tert-butylvinyl) derivative (80% deuterated) were prepared and heated in the gas phase in a static well-conditioned reactor at 280 0 C. The observed normal isotope effect on the 1,3-shift is in the opposite direction from that usually associated with secondary α deuterium isotope effects resulting from changes in bonding, and this inverse isotope effect is thought to arise by induction from the rotational effect on the 1,3-shift. However, the explanation is not consistent with the relatively large rate constant for enantiomerization unless the enantiomerization is a separate process

  2. The effect of dipolar interaction on the magnetic isotope effect

    DEFF Research Database (Denmark)

    Mojaza, Matin; Pedersen, Jørgen Boiden; Lukzen, Nikita

    2010-01-01

    A multi-channel kinetic description is used to study the magnetic isotope effect (MIE) in zero magnetic field. The maximal isotope effect is equal to the number of channels, two for the hyperfine interaction but four for the electron spin dipole–dipole interaction of the intermediate radical pair....... Quantum mechanical calculations agree with these conclusion and show that large MIE may be obtained even in the presence of a strong exchange interaction. The observed magnesium isotope effect on the rate of enzymatic synthesis of adenosine triphosphate (ATP) is approximately 3 implying that the dipolar...... interaction is responsible for the effect. Our calculations provide support for the proposed mechanism....

  3. H/D isotope effects in high temperature proton conductors

    NARCIS (Netherlands)

    Bonanos, N.; Huijser, Jannetje Maria; Poulsen, F.W.

    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

  4. Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

    Science.gov (United States)

    Hin, Remco C.; Coath, Christopher D.; Carter, Philip J.; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A. E.; Willbold, Matthias; Leinhardt, Zoë M.; Walter, Michael J.; Elliott, Tim

    2017-09-01

    It has long been recognized that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and, by inference, the primordial disk from which they formed. However, it is not known whether the notable volatile depletions of planetary bodies are a consequence of accretion or inherited from prior nebular fractionation. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate. Here we develop an analytical approach that corrects a major cause of measurement inaccuracy inherent in conventional methods, and show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour, followed by vapour escape during accretionary growth of planetesimals, generates appropriate residual compositions. Our modelling implies that the isotopic compositions of magnesium, silicon and iron, and the relative abundances of the major elements of Earth and other planetary bodies, are a natural consequence of substantial (about 40 per cent by mass) vapour loss from growing planetesimals by this mechanism.

  5. Magnesium isotope evidence that accretional vapour loss shapes planetary compositions.

    Science.gov (United States)

    Hin, Remco C; Coath, Christopher D; Carter, Philip J; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A E; Willbold, Matthias; Leinhardt, Zoë M; Walter, Michael J; Elliott, Tim

    2017-09-27

    It has long been recognized that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and, by inference, the primordial disk from which they formed. However, it is not known whether the notable volatile depletions of planetary bodies are a consequence of accretion or inherited from prior nebular fractionation. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate. Here we develop an analytical approach that corrects a major cause of measurement inaccuracy inherent in conventional methods, and show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour, followed by vapour escape during accretionary growth of planetesimals, generates appropriate residual compositions. Our modelling implies that the isotopic compositions of magnesium, silicon and iron, and the relative abundances of the major elements of Earth and other planetary bodies, are a natural consequence of substantial (about 40 per cent by mass) vapour loss from growing planetesimals by this mechanism.

  6. Provenance of Chinese Loess: Evidence from Stable Lead Isotope

    Directory of Open Access Journals (Sweden)

    Feng Wu

    2011-01-01

    Full Text Available Twenty-seven samples of typical loess and paleosol strata collected in nine different regions of the Chinese Loess Plateau (CLP were fractionated into PM1.0, PM2.5, PM10 and Total Suspended Particulates (TSP (particulate matter with aerodynamic diameters less than 1.0, 2.5, 10 and ~30 £gm, respectively by a resuspension chamber at the Desert Research Institute (DRI; Reno, NV, United States. The amounts and isotope ratios of lead (Pb were quantified in the loess samples. Our size-segregated analysis demonstrated that the Pb isotopic composition in the loess-paleosol deposits was preserved after grain-size sorting and that therefore the isotope ratio can serve as a proxy for source tracing. A similar pattern of Pb isotope ratios was observed for sediment collected from potential source regions and the loess samples suggested that the Gobi and deserts in southern Mongolia and northern China are major sources for the deposits in the CLP. No significant deviation of Pb isotope amount was found between the nine samples of loess and paleosol strata, implying the stability of loess sources during the glacial and interglacial regime.

  7. Isotopic evidence suggests different initial reaction mechanisms for anaerobic benzene biodegradation.

    Science.gov (United States)

    Mancini, Silvia A; Devine, Cheryl E; Elsner, Martin; Nandi, Monisha E; Ulrich, Ania C; Edwards, Elizabeth A; Lollar, Barbara Sherwood

    2008-11-15

    The initial metabolic reactions for anaerobic benzene biodegradation remain uncharacterized. Isotopic data for carbon and hydrogen fractionation from nitrate-reducing, sulfate-reducing, and methanogenic benzene-degrading enrichment cultures and phylogenic information were used to investigate the initial reaction step in anaerobic benzene biodegradation. Dual parameter plots of carbon and hydrogen isotopic data (deltadelta2H/ deltadelta13C) from each culture were linear, suggesting a consistent reaction mechanism as degradation proceeded. Methanogenic and sulfate-reducing cultures showed consistently higher slopes (m = 29 +/- 2) compared to nitrate-reducing cultures (m = 13 +/- 2) providing evidence for different initial reaction mechanisms. Phylogenetic analyses confirmed that culture conditions were strictly anaerobic, precluding any involvement of molecular oxygen in the observed differences. Using published kinetic data, we explored the possibility of attributing such slopes to reaction mechanisms. The higher slopes found under methanogenic and sulfate-reducing conditions suggest against an alkylation mechanism for these cultures. Observed differences between the methanogenic and nitrate-reducing cultures may not represent distinct reactions of different bonds, but rather subtle differences in relative reaction kinetics. Additional mechanistic conclusions could not be made because kinetic isotope effect data for carboxylation and other putative mechanisms are not available.

  8. Isotopic effects on the phonon modes in boron carbide.

    Science.gov (United States)

    Werheit, H; Kuhlmann, U; Rotter, H W; Shalamberidze, S O

    2010-10-06

    The effect of isotopes ((10)B-(11)B; (12)C-(13)C) on the infrared- and Raman-active phonons of boron carbide has been investigated. For B isotopes, the contributions of the virtual crystal approximation, polarization vector and isotopical disorder are separated. Boron and carbon isotope effects are largely opposite to one another and indicate the share of the particular atoms in the atomic assemblies vibrating in specific phonon modes. Some infrared-active phonons behave as expected for monatomic boron crystals.

  9. Hf isotope evidence for a hidden mantle reservoir

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Simonetti, A.; Stevenson, R.K.

    2002-01-01

    High-precision Hf isotopic analyses and U-Pb ages of carbonatites and kimberlites from Greenland and eastern North America, including Earth's oldest known carbonatite (3 Ga), indicate derivation from an enriched mantle source. This previously unidentified mantle reservoir-marked by an unradiogenic...

  10. Use of isotope effects in the elucidation of aliphatic oxidation as catalyzed by cytochrome P-450

    International Nuclear Information System (INIS)

    Jones, J.P.

    1987-01-01

    Two selectively deuterated n-octanes (octane-1- 2 H 3 and octane-1, 2, 3- 2 H 7 ) were synthesized and subjected to hydroxylation by phenobarbital-induced rat liver microsomes and purified cytochrome P-450b. The results of these experiments provide evidence which clarifies the interplay between a branched reaction pathway and the equilibration of an enzyme-substrate complex, in determining the magnitude of an observed isotope effect. An equation is derived that allows limits to be placed on the intrinsic isotope effect. The intrinsic isotope effect for the formation of 1-octanol was determined by this equation to lie between 9.5 and 9.8. The intramolecular isotope effect for octane-1- 2 H 3 was separated into its primary and secondary components using the method of Hanzlik. The primary effect was found to lie between 7.3 and 7.9 while the secondary effect was found to lie between 1.09-1.14. These data are consistent with a symmetrical reaction coordinate with 15% of the observed isotope effect being due to the secondary effects. A slight deviation from the rule of the geometric means was observed. An identical analysis was performed for ortho, meta and para-xylenes that contained deuterium in one methyl group. The secondary isotope effects varied dramatically, from between 0.93 to 1.19, due to violation of the rule of the geometric mean. The observed isotope effects appeared to vary as a function of the distance between the methyl groups in the various methyl groups of xylene with ortho having the largest isotope effect, meta a median isotope effect or an isotope effect similar in magnitude to ortho, and para the smallest effect

  11. Isotopic evidences for provenances of east asian dust

    International Nuclear Information System (INIS)

    Yang Jiedong; Chen Jun; Li Gaojun; Ji Junfeng; Rao Wenbo

    2007-01-01

    Based on systematical investigations on Nd-Sr isotopes of both the <75μm and <5μm silicate fractions of loess, sand, river and lacustrine sediment samples for ten major deserts, gobi, the Loess Plateau, and the northeast part of the Tibetan-Qinghai Plateau, the following results are obtained. (1) Three isotopic regions of Chinese deserts are identified. Region A (Aland A2), which is the deserts on the northern boundary of China with the highest ε Nd (0)>-7.0. Region B, which is the deserts on the northern margin of Tibetan Plateau with ε Nd (0) ranges form -11.9 to -7.4. Region C, which is the deserts on the Ordos Plateau with the lowest ε nd (0)<-11.5. The distribution of the three isotopic regions is controlled by the tectonic setting in North China. (2) The reliable isotope ranges of the Loess Plateau are 87 Sr/ 86 Sr from 0.71784 to 0.71944, ε Nd (0) from -9.2 to -11.3, which fall in Region B of the Qaiham Desert, Badain Jaran Desert and Tengger Desert. This indicates that the possibility of the Gurbantunggut Desert, Hunlun Buir sandy land, Onqin Daga sandy land, Horqin sandy land, the Hobq Desert and Mu Us Desert, as provenances for the loess are excluded. The isotopic range of the northeast part of the Tibetan-Qinghai Plateau coincides with those of the Badain Jaran Desert and Tengger Desert, and loess in the Loess Plateau, suggesting that the predominant source area of the Loess Plateau is most likely to be the northeast part of the Tibetan-Qinghai Plateau, and the Qaidam Desert, Badain Jaran Desert and Tengger Desert are middle transport stations of loess materials. (3) The comparison with isotopic data of dust extracted from snow deposits at Greenland and sediments of North Pacific confirms the Badain Jaran Desert, Tengger Desert and the Tibetan-Qinghai Plateau to be main source. (4) The analyzed results for dust samples in Beijing region demonstrate that aeolian dust in normal time in 2006 is mostly derived from mixing of Region B and bed rock soil

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  13. Evidence for an ancient osmium isotopic reservoir in Earth.

    Science.gov (United States)

    Meibom, Anders; Frei, Robert

    2002-04-19

    Iridosmine grains from placer deposits associated with peridotite-bearing ophiolites in the Klamath mountains have extremely radiogenic 186Os/188Os ratios and old Re-Os minimum ages, from 256 to 2644 million years. This indicates the existence of an ancient platinum group element reservoir with a supra-chondritic Pt/Os ratio. Such a ratio may be produced in the outer core as a result of inner core crystallization that fractionates Os from Pt. However, if the iridosmine Os isotopic compositions are a signature of the outer core, then the inner core must have formed very early, within several hundred million years after the accretion of Earth.

  14. Isotopic evidence for enhanced fossil fuel sources of aerosol ammonium in the urban atmosphere.

    Science.gov (United States)

    Pan, Yuepeng; Tian, Shili; Liu, Dongwei; Fang, Yunting; Zhu, Xiaying; Gao, Meng; Gao, Jian; Michalski, Greg; Wang, Yuesi

    2018-04-20

    The sources of aerosol ammonium (NH 4 + ) are of interest because of the potential of NH 4 + to impact the Earth's radiative balance, as well as human health and biological diversity. Isotopic source apportionment of aerosol NH 4 + is challenging in the urban atmosphere, which has excess ammonia (NH 3 ) and where nitrogen isotopic fractionation commonly occurs. Based on year-round isotopic measurements in urban Beijing, we show the source dependence of the isotopic abundance of aerosol NH 4 + , with isotopically light (-33.8‰) and heavy (0 to +12.0‰) NH 4 + associated with strong northerly winds and sustained southerly winds, respectively. On an annual basis, 37-52% of the initial NH 3 concentrations in urban Beijing arises from fossil fuel emissions, which are episodically enhanced by air mass stagnation preceding the passage of cold fronts. These results provide strong evidence for the contribution of non-agricultural sources to NH 3 in urban regions and suggest that priority should be given to controlling these emissions for haze regulation. This study presents a carefully executed application of existing stable nitrogen isotope measurement and mass-balance techniques to a very important problem: understanding source contributions to atmospheric NH 3 in Beijing. This question is crucial to informing environmental policy on reducing particulate matter concentrations, which are some of the highest in the world. However, the isotopic source attribution results presented here still involve a number of uncertain assumptions and they are limited by the incomplete set of chemical and isotopic measurements of gas NH 3 and aerosol NH 4 + . Further field work and lab experiments are required to adequately characterize endmember isotopic signatures and the subsequent isotopic fractionation process under different air pollution and meteorological conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Combining solvent isotope effects with substrate isotope effects in mechanistic studies of alcohol and amine oxidation by enzymes.

    Science.gov (United States)

    Fitzpatrick, Paul F

    2015-11-01

    Oxidation of alcohols and amines is catalyzed by multiple families of flavin- and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. This article is part of a Special Issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

    Science.gov (United States)

    Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

    2018-04-01

    Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

  17. Early African Diaspora in colonial Campeche, Mexico: strontium isotopic evidence.

    Science.gov (United States)

    Price, T Douglas; Tiesler, Vera; Burton, James H

    2006-08-01

    Construction activities around Campeche's central park led to the discovery of an early colonial church and an associated burial ground, in use from the mid-16th century AD to the late 17th century. Remains of some individuals revealed dental mutilations characteristic of West Africa. Analyses of strontium isotopes of dental enamel from these individuals yielded unusually high (87)Sr/(86)Sr ratios, inconsistent with an origin in Mesoamerica, but consistent with an origin in West Africa in terrain underlain by the West Africa Craton, perhaps near the port of Elmina, a principal source of slaves for the New World during the 16th century. These individuals likely represent some of the earliest representatives of the African Diaspora in the Americas.

  18. Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes.

    Science.gov (United States)

    Barrick, R E; Showers, W J

    1994-07-08

    The oxygen isotopic composition of vertebrate bone phosphate (delta(p)) is related to ingested water and to the body temperature at which the bone forms. The delta(p) is in equilibrium with the individual's body water, which is at a physiological steady state throughout the body. Therefore, intrabone temperature variation and the mean interbone temperature differences of well-preserved fossil vertebrates can be determined from the deltap variation. Values of delta(p) from a well-preserved Tyrannosaurus rex suggest that this species maintained homeothermy with less than 4 degrees C of variability in body temperature. Maintenance of homeothermy implies a relatively high metabolic rate that is similar to that of endotherms.

  19. Textural and isotopic evidence for Ca-Mg carbonate pedogenesis

    Science.gov (United States)

    Diaz-Hernandez, J. L.; Sánchez-Navas, A.; Delgado, A.; Yepes, J.; Garcia-Casco, A.

    2018-02-01

    Models for evaluating the terrestrial carbon cycle must take into account not only soil organic carbon, represented by a mixture of plant and animal remains, but also soil inorganic carbon, contained in minerals, mainly in calcite and dolomite. Thick soil caliches derived from weathering of mafic and ultramafic rocks must be considered as sinks for carbon storage in soils. The formation of calcite and dolomite from pedogenic alteration of volcanic tephras under an aridic moisture regime is studied in an unusually thick 3-m soil profile on Gran Canaria island (Canary Islands, Spain). The biological activity of the pedogenic environment (soil respiration) releases CO2 incorporated as dissolved inorganic carbon (DIC) in waters. It drives the formation of low-magnesian calcite and calcian dolomite over basaltic substrates, with a δ13C negative signature (-8 to -6‰ vs. V-PDB). Precipitation of authigenic carbonates in the soil is accompanied by the formation of Mg-rich clay minerals and quartz after the weathering of basalts. Mineralogical, textural, compositional, and isotopic variations throughout the soil profile studied indicate that dolomite formed at greater depths and earlier than the calcite. The isotopic signatures of the surficial calcite and deeper dolomite crusts are primary and resulted from the dissolution-precipitation cycles that led to the formation of both types of caliches under different physicochemical conditions. Dolomite formed within a clay-rich matrix through diffusive transport of reactants. It is precipitated from water with more negative δ18O values (-1.5 to -3.5‰ vs. V-SMOW) in the subsoil compared to those of water in equilibrium with surficial calcite. Thus, calcite precipitated after dolomite, and directly from percolating solutions in equilibrium with vadose water enriched in δ18O (-0.5 to +1.5‰) due to the evaporation processes. The accumulation of inorganic carbon reaches 586.1 kg m-2 in the soil studied, which means that the

  20. Energy sources for aquatic animals in the Orinoco River floodplain: evidence from stable isotopes.

    Science.gov (United States)

    Hamilton, S K; Lewis, W M; Sippel, S J

    1992-03-01

    Stable carbon and nitrogen isotope ratios in autotrophs, aquatic invertebrates and fishes from the Orinoco River floodplain of Venezuela reveal that microalgae, including both phytoplankton and epiphytic (attached) forms, are predominant energy sources for many aquatic animals, even though aquatic vascular plants are much more abundant. Floating mats of the grass Paspalum repens and the water hyacinth Eichhornia spp. harbor particularly high densities of aquatic animals, but isotopic evidence indicates that few species are dependent on organic carbon originating from these plants. The stable isotopic evidence for the trophic importance of algae contradicts traditional interpretations of food webs in freshwater wetlands, which are generally thought to be based largely on detritus originating from vascular plants.

  1. Selenium isotope evidence for progressive oxidation of the Neoproterozoic biosphere

    Science.gov (United States)

    Pogge von Strandmann, Philip A. E.; Stüeken, Eva E.; Elliott, Tim; Poulton, Simon W.; Dehler, Carol M.; Canfield, Don E.; Catling, David C.

    2015-01-01

    Neoproterozoic (1,000–542 Myr ago) Earth experienced profound environmental change, including ‘snowball' glaciations, oxygenation and the appearance of animals. However, an integrated understanding of these events remains elusive, partly because proxies that track subtle oceanic or atmospheric redox trends are lacking. Here we utilize selenium (Se) isotopes as a tracer of Earth redox conditions. We find temporal trends towards lower δ82/76Se values in shales before and after all Neoproterozoic glaciations, which we interpret as incomplete reduction of Se oxyanions. Trends suggest that deep-ocean Se oxyanion concentrations increased because of progressive atmospheric and deep-ocean oxidation. Immediately after the Marinoan glaciation, higher δ82/76Se values superpose the general decline. This may indicate less oxic conditions with lower availability of oxyanions or increased bioproductivity along continental margins that captured heavy seawater δ82/76Se into buried organics. Overall, increased ocean oxidation and atmospheric O2 extended over at least 100 million years, setting the stage for early animal evolution. PMID:26679529

  2. Isotopic evidence for the diverse origins of nitrate minerals

    International Nuclear Information System (INIS)

    Heaton, T.H.E.

    1987-01-01

    Nitrate minerals are rare and, apart from their occasional value as economic deposits of fertilizer, not of general importance in geology. The mechanisms by which they are formed, however, are still the subject of considerable debate. This brief discussion indicates that the study of the 15 N/ 14 N ratios of nitrate minerals can yield useful information on their origins. The low 15 N/ 14 N ratios for nitrate in desert environments indicate that soil or animal waste sources of nitrogen are unlikely. Derivation from atmospheric precipitation is consistent with the presently limited knowledge of the isotopic characteristics of atmospheric compounds, but can only be confirmed when data for these compounds in desert areas become available. For nitrates in wetter environments the 15 N/ 14 N ratios indicate that atmospheric sources are not important, and that the formation of nitrate from gaseous ammonia emanating from animal waste is probably not a significant mechanism. The nitrate appears to be chiefly derived either by direct solution of animal waste nitrate (Lydenburg cave and Prieskapoort) or from soil-derived nitrate brought in by groundwater (Autana and possibly Abjaterskop caves). In the case of Sveite special conditions involving bacterial processes are also implied

  3. Isotopic effect on thermal physical properties of isotopically modified boron single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Quanli [Japan Science and Technology Corporation, Kawaguchi, Saitama (Japan); Noda, Tetsuji; Suzuki, Hiroshi; Araki, Hiroshi; Numazawa, Takenori; Hirano, Toshiyuki [National Institute for Materials Science, Tsukuba, Ibaraki (Japan); Nogi, Naoyuki; Tanaka, Satoru [University of Tokyo, Department of Quantum Engineering and Systems Science, Tokyo (Japan)

    2002-04-01

    The measurement of specific heat and thermal conductivity at low temperature for isotopically modified boron single crystals was performed between 0.5 and 100K using relaxation method and steady heat flow method, respectively. The results indicate that the specific heat has obvious divergences at T<5K. At 40K, the thermal conductivity of {sup 10}B-enriched crystal is about 570 W/m{center_dot}K, which is 40% larger than that of natural boron crystal. The influence of lattice vibration modes and the isotopic effect on specific heat and thermal conductivity for isotopically modified boron are discussed. (author)

  4. Uses of isotope effects in the study of enzymes.

    Science.gov (United States)

    Northrop, D B

    2001-06-01

    There have been few recent additions to the technical methods employed in the study of isotope effects, notable exceptions being the use of high pressure as an experimental variable and the measurement of heavy-atom isotope effects on maximal velocities using continuous-flow techniques. Most of the innovations are in the realm of new experimental designs that allow the asking of new questions. These designs include the use of isotope effects to: determine kinetic mechanisms, distinguish between changes in enzymatic activity and loss of active enzyme, distinguish between reactant-state origins and transition-state origins and quantify hydrogen tunneling, separate and quantify multiple origins of solvent isotope effects, distinguish between concerted and stepwise chemical mechanisms, characterize bond order changes in ligand binding, distinguish different pathways of inhibitor binding, and estimate intrinsic isotope effects. Copyright 2001 Academic Press.

  5. Sr Isotopic Evidence on the Spilitic Degradation of the Deccan Basalt

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 109; Issue 1. Sr Isotopic Evidence on the Spilitic Degradation ... In contrast, a dramatic increase in the rare earth elements (REE) from basalt to spilite is rather puzzling as rare earths are considered to be relatively immobile. The geochemistry thus suggests that the ...

  6. Three Gorges Dam alters the Changjiang (Yangtze) river water cycle in the dry seasons: Evidence from H-O isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Kai [School of Ocean and Earth Science, Tongji University, Shanghai, 200092 (China); State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092 (China); Yang, Shouye, E-mail: syyang@tongji.edu.cn [State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092 (China); Laboratory for Marine Geology, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266061 (China); Lian, Ergang [School of Ocean and Earth Science, Tongji University, Shanghai, 200092 (China); State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092 (China); Li, Chao [State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092 (China); Yang, Chengfan; Wei, Hailun [School of Ocean and Earth Science, Tongji University, Shanghai, 200092 (China); State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092 (China)

    2016-08-15

    As the largest hydropower project in the world, the Three Gorges Dam (TGD) has attracted great concerns in terms of its impact on the Changjiang (Yangtze) River and coastal marine environments. In this study, we measured or collected the H-O isotopic data of river water, groundwater and precipitation in the mid-lower Changjiang catchment during the dry seasons of recent years. The aim was to investigate the changes of river water cycle in response to the impoundment of the TGD. Isotopic evidences suggested that the mid-lower Changjiang river water was ultimately derived from precipitation, but dominated by the mixing of different water masses with variable sources and isotopic signals as well. The isotopic parameter “deuterium excess” (d-excess) yielded large fluctuations along the mid-lower mainstream during the initial stage of the TGD impoundment, which was inherited from the upstream water with inhomogeneous isotopic signals. However, as the reservoir water level rising to the present stage, small variability of d-excess was observed along the mid-lower mainstream. This discrepancy could be explained that the TGD impoundment had significantly altered the water cycle downstream the dam, with the rising water level increasing the residence time and enhancing the mixing of reservoir water derived from upstream. This eventually resulted in the homogenization of reservoir water, and thus small fluctuations of d-excess downstream the dam after the quasi-normal stage (2008 to present). We infer that the retention effect of large reservoirs has greatly buffered the d-excess natural variability of water cycle in large river systems. Nevertheless, more research attention has to be paid to the damming effect on the water cycle in the river, estuarine and coastal areas, especially during the dry seasons. - Highlights: • Stable H-O isotopes indicate the Changjiang river water cycle in dry seasons. • The isotopic parameter “d-excess” reveals the origins of

  7. Bromine and carbon isotope effects during photolysis of brominated phenols.

    Science.gov (United States)

    Zakon, Yevgeni; Halicz, Ludwik; Gelman, Faina

    2013-12-17

    In the present study, carbon and bromine isotope effects during UV-photodegradation of bromophenols in aqueous and ethanolic solutions were determined. An anomalous relatively high inverse bromine isotope fractionation (εreactive position up to +5.1‰) along with normal carbon isotope effect (εreactive position of -12.6‰ to -23.4‰) observed in our study may be attributed to coexistence of both mass-dependent and mass-independent isotope fractionation of C-Br bond cleavage. Isotope effects of a similar scale were observed for all the studied reactions in ethanol, and for 4-bromophenol in aqueous solution. This may point out related radical mechanism for these processes. The lack of any carbon and bromine isotope effects during photodegradation of 2-bromophenol in aqueous solution possibly indicates that C-Br bond cleavage is not a rate-limiting step in the reaction. The bromine isotope fractionation, without any detectable carbon isotope effect, that was observed for 3-bromophenol photolysis in aqueous solution probably originates from mass-independent fractionation.

  8. Lunar tungsten isotopic evidence for the late veneer.

    Science.gov (United States)

    Kruijer, Thomas S; Kleine, Thorsten; Fischer-Gödde, Mario; Sprung, Peter

    2015-04-23

    According to the most widely accepted theory of lunar origin, a giant impact on the Earth led to the formation of the Moon, and also initiated the final stage of the formation of the Earth's core. Core formation should have removed the highly siderophile elements (HSE) from Earth's primitive mantle (that is, the bulk silicate Earth), yet HSE abundances are higher than expected. One explanation for this overabundance is that a 'late veneer' of primitive material was added to the bulk silicate Earth after the core formed. To test this hypothesis, tungsten isotopes are useful for two reasons: first, because the late veneer material had a different (182)W/(184)W ratio to that of the bulk silicate Earth, and second, proportionally more material was added to the Earth than to the Moon. Thus, if a late veneer did occur, the bulk silicate Earth and the Moon must have different (182)W/(184)W ratios. Moreover, the Moon-forming impact would also have created (182)W differences because the mantle and core material of the impactor with distinct (182)W/(184)W would have mixed with the proto-Earth during the giant impact. However the (182)W/(184)W of the Moon has not been determined precisely enough to identify signatures of a late veneer or the giant impact. Here, using more-precise measurement techniques, we show that the Moon exhibits a (182)W excess of 27 ± 4 parts per million over the present-day bulk silicate Earth. This excess is consistent with the expected (182)W difference resulting from a late veneer with a total mass and composition inferred from HSE systematics. Thus, our data independently show that HSE abundances in the bulk silicate Earth were established after the giant impact and core formation, as predicted by the late veneer hypothesis. But, unexpectedly, we find that before the late veneer, no (182)W anomaly existed between the bulk silicate Earth and the Moon, even though one should have arisen through the giant impact. The origin of the homogeneous (182

  9. Isotope hydrological evidence of geomorphological changes in North-Eastern Hungary

    International Nuclear Information System (INIS)

    Hertelendi, E.; Marton, L.; Miko, L.

    1991-01-01

    Stable isotope and radiocarbon data of groundwater stored in Quaternary aquifers in North-Eastern Hungary can not be explained by climatic changes alone. More than two hundred δD, δ 18 O and radiocarbon ages of waters from 79 wells show that the recharge are changed during the time of upper pleniglacial and late glacial. Groundwaters of the studied are can be divided into three categories, which can explain their origin. The data are consistent with geomorphological results giving isotope evidence of hydrology for a geodynamical event during the mentioned periods. (R.P.) 3 refs.; 2 figs

  10. Great isotope effects in compounding of sodium isotopes by macrocyclic polyether

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1978-01-01

    Isotope effects appear in the compounding of the two sodium isotopes 24 Na + and 22 Na + with macrocyclic polyethers, whose value was determined for the 13 best known polyethers. A radiometric process was used for determining the different half life periods of the nuclides used. To separate the compound and non-compound types, these were distributed between water and chloroform. The isotope ratio in the chloroform phase was compared with the output isotope ratio and the separation facfor determined from this. When using crown ethers, there was enrichment of 24 Na + by a significant amount (large crown ether) up to 3.1 +- 0.4% for 18 crown 6. The remarkably high results can be correlated by Biegeleisen's theory with other chemical conditions. There is a report on the first results of transferring these conditions to the H + /T + system. (orig.) [de

  11. Isotope effect in the Knight shift of potassium

    International Nuclear Information System (INIS)

    Sahm, W.; Schwenk, A.

    1975-01-01

    The Knight shifts of the potassium isotopes 39 K and 41 K were determined with high accuracy: Ksup((39)) = 0.274 35(10)% and Ksup((41)) = 0.274 93(12)%. The relative isotope effect ΔK/K = -0.210 (20)% is in agreement with the hyperfine structure anomaly 39 Δ 41 . (orig.) [de

  12. Stable isotope evidence for the environmental impact of a land-based fish farm in the western Mediterranean

    International Nuclear Information System (INIS)

    Vizzini, Salvatrice; Mazzola, Antonio

    2004-01-01

    Isotopic examination (δ 13 C and δ 15 N) of organic matter sources and consumers was used to assess the impact and trace the dispersal of wastewater from a land-based fish farm in western Mediterranean. The results provide evidence of the non-negligible effect of aquaculture facilities on the natural stable isotopic composition of organisms. Aquaculture waste entered the food web, altering the natural isotopic composition of organic matter sources at the base and the upper trophic levels. Nitrogen-rich fish waste mainly affected δ 15 N values, while δ 13 C showed less alteration. Waste seemed to disperse widely enough to affect the isotopic composition at the study site about 500 m from the outfall, while sites at 1 and 2 km from the outfall showed values that were similar to each other and different from those of the impacted site. The impact was detected at different ecosystem levels, although primary producers were more affected by fish farm waste taking up aquaculture-derived nutrients

  13. Stable isotope evidence for increasing dietary breadth in the European mid-Upper Paleolithic.

    Science.gov (United States)

    Richards, M P; Pettitt, P B; Stiner, M C; Trinkaus, E

    2001-05-22

    New carbon and nitrogen stable isotope values for human remains dating to the mid-Upper Paleolithic in Europe indicate significant amounts of aquatic (fish, mollusks, and/or birds) foods in some of their diets. Most of this evidence points to exploitation of inland freshwater aquatic resources in particular. By contrast, European Neandertal collagen carbon and nitrogen stable isotope values do not indicate significant use of inland aquatic foods but instead show that they obtained the majority of their protein from terrestrial herbivores. In agreement with recent zooarcheological analyses, the isotope results indicate shifts toward a more broad-spectrum subsistence economy in inland Europe by the mid-Upper Paleolithic period, probably associated with significant population increases.

  14. Mercury Isotopic Evidence for Contrasting Mercury Transport Pathways to Coastal versus Open Ocean Fisheries (Invited)

    Science.gov (United States)

    Blum, J. D.; Senn, D. B.; Chesney, E. J.; Bank, M. S.; Maage, A.; Shine, J. P.

    2009-12-01

    Mercury stable isotopes provide a new method for tracing the sources and chemical transformations of Hg in the environment. In this study we used Hg isotopes to investigate Hg sources to coastal versus migratory open-ocean species of fish residing in the northern Gulf of Mexico (nGOM). We report Hg isotope ratios as δ202Hg (mass dependent fractionation relative to NIST 3133) and Δ201Hg (mass independent fractionation of odd isotopes). In six coastal and two open ocean species (blackfin and yellowfin tuna), Hg isotopic compositions fell into two non-overlapping ranges. The tuna had significantly higher δ202Hg (0.1 to 0.7‰) and Δ201Hg (1.0 to 2.2‰) than the coastal fish (δ202Hg = 0 to -1.0‰; Δ201Hg = 0.4 to 0.5‰). The observations can be best explained by largely disconnected food webs with isotopically distinct MeHg sources. The ratio Δ199Hg/Δ201Hg in nGOM fish is 1.30±0.10 which is consistent with laboratory studies of photochemical MeHg degradation and with ratios measured in freshwater fish (Bergquist and Blum, 2007). The magnitude of mass independent fractionation of Hg in the open-ocean fish suggests that this source of MeHg was subjected to extensive photodegradation (~50%) before entering the base of the open-ocean food web. Given the Mississippi River’s large, productive footprint in the nGOM and the potential for exporting prey and MeHg to the adjacent oligotrophic GOM, the different MeHg sources are noteworthy and consistent with recent evidence in other systems of important open-ocean MeHg sources. Bergquist, B. A. and Blum, J. D., 2007. Mass-dependent and -independent fractionation of Hg isotopes by photoreduction in aquatic systems. Science 318, 417-420.

  15. Biosynthetic effects on the stable carbon isotopic compositions of agal lipids: Implications for deciphering the carbon isotopic biomarker record

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Klein Breteler, W.C.M.; Blokker, P.; Schogt, N.; Rijpstra, W.I.C.; Grice, K.; Baas, M.

    1998-01-01

    Thirteen species of algae covering an extensive range of classes were cultured and stable carbon isotopic compositions of their lipids were analysed in order to assess carbon isotopic fractionation effects during their biosynthesis. The fatty acids were found to have similar stable carbon isotopic

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

    Science.gov (United States)

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

    2011-01-01

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

  17. Lithium-isotope evidence for enhanced silicate weathering during OAE 1a (Early Aptian Selli event)

    Science.gov (United States)

    Lechler, Maria; Pogge von Strandmann, Philip A. E.; Jenkyns, Hugh C.; Prosser, Giacomo; Parente, Mariano

    2015-12-01

    An abrupt rise in temperature, forced by a massive input of CO2 into the atmosphere, is commonly invoked as the main trigger for Oceanic Anoxic Events (OAEs). Global warming initiated a cascade of palaeoenvironmental perturbations starting with increased continental weathering and an accelerated hydrological cycle that delivered higher loads of nutrients to coastal areas, stimulating biological productivity. The end-result was widespread anoxia and deposition of black shales: the hallmarks of OAEs. In order to assess the role of weathering as both an OAE initiator and terminator (via CO2 sequestration) during the Early Aptian OAE 1a (Selli Event, ∼120 Ma) the isotopic ratio of lithium isotopes was analysed in three sections of shallow-marine carbonates from the Pacific and Tethyan realms and one basinal pelagic section from the Tethyan domain. Because the isotopic composition of lithium in seawater is largely controlled by continental silicate weathering and high- and low-temperature alteration of basaltic material, a shift to lighter δ7Li values is expected to characterize OAEs. The studied sections illustrate this phenomenon: δ7Li values decrease to a minimum coincident with the negative carbon-isotope excursion that effectively records the onset of OAE 1a. A second negative δ7Li excursion occurs coeval with the minimum in strontium isotopes after the event. The striking similarity to the strontium-isotope record argues for a common driver. The formation and destruction (weathering) of an oceanic LIP could account for the parallel trend in both isotope systems. The double-spike in lithium isotopes is probably related to a change in weathering congruencies. Such a chemostratigraphy is consistent with the hypothesis that an increase in silicate weathering, in conjunction with organic-carbon burial, led to drawdown of atmospheric CO2 during the early Aptian OAE 1a.

  18. Isotopic evidence for climatic conditions in Southeast Asia at the last glacial maximum

    International Nuclear Information System (INIS)

    Aggarwal, P.K.; Gibson, J.J.; Kulkarni, K.M.; Froehlich, K.

    2002-01-01

    Stable isotope composition of dated groundwater archives from the Philippines, Vietnam, Thailand and Bangladesh trace changes in monsoon conditions, primarily rainout processes between the Last Glacial Maximum (LGM) and present day in southeast Asia. Today, isotope-climate relations are well established by the IAEA/WMO Global Network of Isotopes in Precipitation survey which reveals more depleted δ 18 O and δ 2 H for the Pacific Ocean monsoon regime than for the Indian Ocean monsoon regime, primarily due to proximal ocean sources and subdued continental moisture recycling for the latter region. Groundwater archives, reflecting past isotopic composition of precipitation, strongly suggest that this distinction was preserved or slightly enhanced at the time of the LGM, despite an apparent weakening of the summer monsoon and associated rainout processes. Overall, precipitation and moisture recycling, and enhanced continental effects are inferred to be the primary controls on δ 18 O signals in groundwater in southeast Asia. Comparison of groundwater isotope signatures and an ECHAM4 model simulation of the isotopic distribution in precipitation at 21ka reveal similar patterns, but the impacts of increased air mass contributions from high latitudes and reduced Eurasian moisture recycling at the LGM are shown to be potentially greater for the Pacific region than predicted by the model. (author)

  19. Gyrokinetic characterization of the isotope effect in turbulent transport at the FT-2 tokamak

    Science.gov (United States)

    Niskala, P.; Gurchenko, A. D.; Gusakov, E. Z.; Altukhov, A. B.; Esipov, L. A.; Kantor, M. Yu; Kiviniemi, T. P.; Kouprienko, D.; Korpilo, T.; Lashkul, S. I.; Leerink, S.; Perevalov, A. A.; Rochford, R.

    2017-04-01

    Isotope effect allows fusion devices to perform better when heavier hydrogen isotopes are used as fuel, but the reason for this improvement is not yet understood. We present the first direct evidence of the isotope effect on particle confinement in the FT-2 tokamak and investigate it via gyrokinetic simulations. Experimental measurements for comparable hydrogen and deuterium discharges show that the particle confinement time increases by 40% for the heavier isotope species. The isotope effect on particle flux is reproduced in global and local gyrokinetic simulations. Global ELMFIRE simulations demonstrate a systemic reduction in particle fluxes across the radial range, showing a ratio of fluxes {{{Γ }}}{{H}}/{{{Γ }}}{{D}}=1.3 at the edge and {{{Γ }}}{{H}}/{{{Γ }}}{{D}}=1.4 at r/a=0.6. Local GENE simulations agree qualitatively with the result. Besides the fluctuation level, smaller scales and a favorable shift in the cross-phase between the turbulent fluctuations are found to contribute to the isotope effect in the simulations.

  20. Medical applications of Cu, Zn, and S isotope effects.

    Science.gov (United States)

    Albarede, Francis; Télouk, Philippe; Balter, Vincent; Bondanese, Victor P; Albalat, Emmanuelle; Oger, Philippe; Bonaventura, Paola; Miossec, Pierre; Fujii, Toshiyuki

    2016-10-01

    This review examines recent applications of stable copper, zinc and sulfur isotopes to medical cases and notably cancer. The distribution of the natural stable isotopes of a particular element among coexisting molecular species varies as a function of the bond strength, the ionic charge, and the coordination, and it also changes with kinetics. Ab initio calculations show that compounds in which a metal binds to oxygen- (sulfate, phosphate, lactate) and nitrogen-bearing moieties (histidine) favor heavy isotopes, whereas bonds with sulfur (cysteine, methionine) favor light isotopes. Oxidized cations (e.g., Cu(ii)) and low coordination numbers are expected to favor heavy isotopes relative to their reduced counterparts (Cu(i)) and high coordination numbers. Here we discuss the first observations of Cu, Zn, and S isotopic variations, three elements closely related along multiple biological pathways, with emphasis on serum samples of healthy volunteers and of cancer patients. It was found that heavy isotopes of Zn and to an even greater extent Cu are enriched in erythrocytes relative to serum, while the difference is small for sulfur. Isotopic variations related to age and sex are relatively small. The 65 Cu/ 63 Cu ratio in the serum of patients with colon, breast, and liver cancer is conspicuously low relative to healthy subjects. The characteristic time over which Cu isotopes may change with disease progression (a few weeks) is consistent with both the turnover time of the element and albumin half-life. A parallel effect on sulfur isotopes is detected in a few un-medicated patients. Copper in liver tumor tissue is isotopically heavy. In contrast, Zn in breast cancer tumors is isotopically lighter than in healthy breast tissue. 66 Zn/ 64 Zn is very similar in the serum of cancer patients and in controls. Possible reasons for Cu isotope variations may be related to the cytosolic storage of Cu lactate (Warburg effect), release of intracellular copper from cysteine

  1. Kinetic 15N-isotope effects on algal growth

    Science.gov (United States)

    Andriukonis, Eivydas; Gorokhova, Elena

    2017-03-01

    Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in 15N-enriched media. With increasing 15N concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high 15N environment may exist. Remarkably, the lag-phase response at 3.5 at% 15N was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

  2. Entering chloride kinetic isotope effects in protic and aprotic solvents

    International Nuclear Information System (INIS)

    Cromartie, T.H.; Swain, C.G.

    1976-01-01

    Chlorine kinetic isotope effects for the reaction of ethylene oxide and chloride ion are normal ( 35 Cl/ 37 Cl greater than unity) in protic solvents and in acetone and dimethylformamide (DMF) in the presence of 1 equiv of 2,6-lutidinium ion. In the presence of 0.1 equiv of this cation (and 0.9 of Li + ) the isotope effect in DMF is inverse (0.9922). This is the first observation of an inverse entering-group heavy-atom isotope effect. The reaction of chloride ion with dimethyl sulfate is normal in water but inverse in DMF. The ''normal'' isotope effects are shown to be due in large measure to the dominance of changes in hydrogen bonding to chlorine over changes in carbon--chlorine bonding

  3. Clumped isotope effects during OH and Cl oxidation of methane

    DEFF Research Database (Denmark)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

    2017-01-01

    A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... was produced from the reaction of O(1D) (from O3 photolysis) with H2O, and Cl was from photolysis of Cl2. Samples were taken from the reaction cell and analyzed for methane (12CH4, 12CH3D, 13CH4, 13CH3D) isotopologue ratios using tunable infrared laser direct absorption spectroscopy. Measured kinetic isotope...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...

  4. Human mobility and the prehistoric spread of farming: isotope evidence from human skeletons

    OpenAIRE

    Bentley, Alex

    2004-01-01

    For over a century, archaeologists, linguists and, more recently, geneticists have debated whether the earliest farmers in Europe and elsewhere were migrants to new regions, whether indigenous hunter-gatherers adopted farming, or whether both processes combined as the two groups intermarried. Now analysis of isotopes in archaeologically recovered skeletons is providing new evidence about the mobility of some of the earliest farmers in central Europe and Southeast Asia.

  5. Human mobility and the prehistoric spread of farming: isotope evidence from human skeletons

    Directory of Open Access Journals (Sweden)

    Alex Bentley

    2004-08-01

    Full Text Available For over a century, archaeologists, linguists and, more recently, geneticists have debated whether the earliest farmers in Europe and elsewhere were migrants to new regions, whether indigenous hunter-gatherers adopted farming, or whether both processes combined as the two groups intermarried. Now analysis of isotopes in archaeologically recovered skeletons is providing new evidence about the mobility of some of the earliest farmers in central Europe and Southeast Asia.

  6. Solvent isotope effects in the complex formation of beryllium sulphate

    International Nuclear Information System (INIS)

    Boojj, M.

    1978-01-01

    The kinetics of complex formation and dissociation of BeSO 4 in D 2 O has been studied. The association constant and the inner sphere/outer sphere equilibrium constant were obtained. By comparing with the corresponding results in H 2 O(1) the solvent isotope effect could be evaluated for some of the involved thermodynamic and kinetic constants. The isotope effects can be understood in terms of Swain and Bader's statistical thermodynamical calculations (2). (orig.) [de

  7. Absence of isotope effect of diffusion in a metallic glass

    International Nuclear Information System (INIS)

    Heesemann, A.; Raetzke, K.; Faupel, F.; Hoffmann, J.; Heinemann, K.

    1995-01-01

    The isotope effect E = d ln(D)/d ln (1/√m) of Co diffusion in structurally relaxed Co 86 Zr 14 and Co 81 Zr 19 glasses has been measured by means of a radiotracer technique. Within experimental accuracy no isotope effect was detected (E < 0.04). This suggests a highly cooperative diffusion mechanism. The connection between diffusion and collective low-frequency relaxations in glasses is discussed. (orig.)

  8. Platinum isotopes in iron meteorites: Galactic cosmic ray effects and nucleosynthetic homogeneity in the p-process isotope 190Pt and the other platinum isotopes

    Science.gov (United States)

    Hunt, Alison C.; Ek, Mattias; Schönbächler, Maria

    2017-11-01

    Platinum isotopes are sensitive to the effects of galactic cosmic rays (GCR), which can alter isotope ratios and mask nucleosynthetic isotope variations. Platinum also features one p-process isotope, 190Pt, which is very low abundance and therefore challenging to analyse. Platinum-190 is relevant for early solar-system chronology because of its decay to 186Os. Here, we present new Pt isotope data for five iron meteorite groups (IAB, IIAB, IID, IIIAB and IVA), including high-precision measurements of 190Pt for the IAB, IIAB and IIIAB irons, determined by multi-collector ICPMS. New data are in good agreement with previous studies and display correlations between different Pt isotopes. The slopes of these correlations are well-reproduced by the available GCR models. We report Pt isotope ratios for the IID meteorite Carbo that are consistently higher than the predicted effects from the GCR model. This suggests that the model predictions do not fully account for all the GCR effects on Pt isotopes, but also that the pre-atmospheric radii and exposure times calculated for Carbo may be incorrect. Despite this, the good agreement of relative effects in Pt isotopes with the predicted GCR trends confirms that Pt isotopes are a useful in-situ neutron dosimeter. Once GCR effects are accounted for, our new dataset reveals s- and r-process homogeneity between the iron meteorite groups studied here and the Earth. New 190Pt data for the IAB, IIAB and IIIAB iron meteorites indicate the absence of GCR effects and homogeneity in the p-process isotope between these groups and the Earth. This corresponds well with results from other heavy p-process isotopes and suggests their homogenous distribution in the inner solar system, although it does not exclude that potential p-process isotope variations are too diluted to be currently detectable.

  9. Diversity of management strategies in Mesoamerican turkeys: archaeological, isotopic and genetic evidence.

    Science.gov (United States)

    Manin, Aurelie; Corona-M, Eduardo; Alexander, Michelle; Craig, Abigail; Thornton, Erin Kennedy; Yang, Dongya Y; Richards, Michael; Speller, Camilla F

    2018-01-01

    The turkey ( Meleagris gallopavo ) represents one of the few domestic animals of the New World. While current research points to distinct domestication centres in the Southwest USA and Mesoamerica, several questions regarding the number of progenitor populations, and the timing and intensity of turkey husbandry remain unanswered. This study applied ancient mitochondrial DNA and stable isotope ( δ 13 C, δ 15 N) analysis to 55 archaeological turkey remains from Mexico to investigate pre-contact turkey exploitation in Mesoamerica. Three different (sub)species of turkeys were identified in the archaeological record ( M. g. mexicana , M. g. gallopavo and M. ocellata ), indicating the exploitation of diverse local populations, as well as the trade of captively reared birds into the Maya area. No evidence of shared maternal haplotypes was observed between Mesoamerica and the Southwest USA, in contrast with archaeological evidence for trade of other domestic products. Isotopic analysis indicates a range of feeding behaviours in ancient Mesoamerican turkeys, including wild foraging, human provisioning and mixed feeding ecologies. This variability in turkey diet decreases through time, with archaeological, genetic and isotopic evidence all pointing to the intensification of domestic turkey management and husbandry, culminating in the Postclassic period.

  10. Diversity of management strategies in Mesoamerican turkeys: archaeological, isotopic and genetic evidence

    Science.gov (United States)

    Manin, Aurelie; Corona-M, Eduardo; Craig, Abigail; Thornton, Erin Kennedy; Yang, Dongya Y.; Richards, Michael

    2018-01-01

    The turkey (Meleagris gallopavo) represents one of the few domestic animals of the New World. While current research points to distinct domestication centres in the Southwest USA and Mesoamerica, several questions regarding the number of progenitor populations, and the timing and intensity of turkey husbandry remain unanswered. This study applied ancient mitochondrial DNA and stable isotope (δ13C, δ15N) analysis to 55 archaeological turkey remains from Mexico to investigate pre-contact turkey exploitation in Mesoamerica. Three different (sub)species of turkeys were identified in the archaeological record (M. g. mexicana, M. g. gallopavo and M. ocellata), indicating the exploitation of diverse local populations, as well as the trade of captively reared birds into the Maya area. No evidence of shared maternal haplotypes was observed between Mesoamerica and the Southwest USA, in contrast with archaeological evidence for trade of other domestic products. Isotopic analysis indicates a range of feeding behaviours in ancient Mesoamerican turkeys, including wild foraging, human provisioning and mixed feeding ecologies. This variability in turkey diet decreases through time, with archaeological, genetic and isotopic evidence all pointing to the intensification of domestic turkey management and husbandry, culminating in the Postclassic period. PMID:29410864

  11. 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.

  12. Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

    Science.gov (United States)

    Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.

    2009-01-01

    The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced

  13. Isotope separation factor and kinetic isotope effect of the hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Krishtalik, L.I.

    2001-01-01

    In the framework of junified approach the experimentally observed dependences of kinetic isotopic effects (KIE) of the reaction of hydrogen electrolytic evolution on the value of potential on electrode were explained. It is shown that hydrogen isotope separation factor depends on KIE for two stages of the reaction, i.e. discharge on the electrode and electrochemical desorption, moreover, decrease in KIE with potential for the desorption stage overbalances its growth for the discharge stage. The reason for KIE decrease is non-activation character of the process, therefore, there is no dependence on potential of relative contribution of the product vibration-excited states [ru

  14. Bibliography on vapor pressure isotope effects

    International Nuclear Information System (INIS)

    Jancso, G.

    1980-04-01

    The first Bibliography on Vapour Pressure Isotope and covered the literature of the period from 1919 through December 1975. The present Supplement reviews the literature from January 1976 through December 1979. The bibliography is arranged in chronological order; within each year the references are listed alphabetically according to the name of the first author of each work. (author)

  15. Multiple-sulfur isotope effects during photolysis of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    Y. Lin

    2011-10-01

    Full Text Available Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS to carbon monoxide (CO and elemental sulfur (S0. The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5‰ when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3‰. The observed triple isotope coefficients are ln(δ34S + 1/ln(δ34S + 1 = 0.534 ± 0.005 and ln(δ36S + 1/ln(δ34S + 1 = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10‰ for 34S/32S, and can be the major source of background stratospheric sulfate aerosol (SSA during volcanic quiescence.

  16. Compound-specific Isotope Analysis of Cyanobacterial Pure cultures and Microbial Mats: Effects of Photorespiration?

    Science.gov (United States)

    Jahnke, L. L.; Summons, R. E.

    2006-01-01

    Microbial mats are considered modern homologs of Precambrian stromatolites. The carbon isotopic compositions of organic matter and biomarker lipids provide clues to the depositional environments of ancient mat ecosystems. As the source of primary carbon fixation for over two billion years, an understanding of cyanobacterial lipid biosynthesis, associated isotopic discriminations, and the influence of physiological factors on growth and isotope expression is essential to help us compare modern microbial ecosystems to their ancient counterparts. Here, we report on the effects of photorespiration (PR) on the isotopic composition of cyanobacteria and biomarker lipids, and on potential PR effects associated with the composition of various microbial mats. The high light, high O2 and limiting CO2 conditions often present at the surface of microbial mats are known to support PR in cyanobacteria. The oxygenase function of ribulose bisphosphate carboxylase/oxygenase can result in photoexcretion of glycolate and subsequent degration by heterotrophic bacteria. We have found evidence which supports an isotopic depletion (increased apparent E) scaled to O2 level associated with growth of Phormidium luridum at low CO2 concentrations (less than 0.04%). Similar to previous studies, isotopic differences between biomass and lipid biomarkers, and between lipid classes were positively correlated with overall fractionation, and should provide a means of estimating the influence of PR on overall isotopic composition of microbial mats. Several examples of microbial mats growing in the hydrothermal waters of Yellowstone National Park and the hypersaline marine evaporation ponds at Guerrero Negro, Baja Sur Mexico will be compared with a view to PR as a possible explanation of the relatively heavy C-isotope composition of hypersaline mats.

  17. Isotopic evidence of plutonium release into the environment from the Fukushima DNPP accident

    Science.gov (United States)

    Zheng, Jian; Tagami, Keiko; Watanabe, Yoshito; Uchida, Shigeo; Aono, Tatsuo; Ishii, Nobuyoshi; Yoshida, Satoshi; Kubota, Yoshihisa; Fuma, Shoichi; Ihara, Sadao

    2012-01-01

    The Fukushima Daiichi nuclear power plant (DNPP) accident caused massive releases of radioactivity into the environment. The released highly volatile fission products, such as 129mTe, 131I, 134Cs, 136Cs and 137Cs were found to be widely distributed in Fukushima and its adjacent prefectures in eastern Japan. However, the release of non-volatile actinides, in particular, Pu isotopes remains uncertain almost one year after the accident. Here we report the isotopic evidence for the release of Pu into the atmosphere and deposition on the ground in northwest and south of the Fukushima DNPP in the 20–30 km zones. The high activity ratio of 241Pu/239+240Pu (> 100) from the Fukushima DNPP accident highlights the need for long-term 241Pu dose assessment, and the ingrowth of 241Am. The results are important for the estimation of reactor damage and have significant implication in the strategy of decontamination. PMID:22403743

  18. Isotopic phonon effects in β-rhombohedral boron--non-statistical isotope distribution.

    Science.gov (United States)

    Werheit, H; Filipov, V; Kuhlmann, U; Schwarz, U; Armbrüster, M; Antadze, M

    2012-05-02

    On the basis of the spectra of IR- and Raman-active phonons, the isotopic phonon effects in β-rhombohedral boron are analysed for polycrystalline (10)B- and (11)B-enriched samples of different origin and high-purity (nat)B single crystals. Intra- and inter-icosahedral B-B vibrations are harmonic, hence meeting the virtual crystal approximation (VCA) requirements. Deviations from the phonon shift expected according to the VCA are attributed to the anharmonic share of the lattice vibrations. In the case of icosahedral vibrations, the agreement with calculations on α-rhombohedral boron by Shirai and Katayama-Yoshida is quite satisfactory. Phonon shifts due to isotopic disorder in (nat)B are separated and determined. Some phonon frequencies are sensitive to impurities. The isotopic phonon effects yield valuable specific information on the nature of the different phonon modes. The occupation of regular boron sites by isotopes deviates significantly from the random distribution. © 2012 IOP Publishing Ltd

  19. Isotope effects in hydrogen atom transfers. 9. Neighboring group participation

    International Nuclear Information System (INIS)

    Lewis, E.S.; Shen, C.C.

    1977-01-01

    The tritium isotope effects in hydrogen abstraction by bromine atoms from HC(Me) 2 CH 2 X have been measured in the photobromination reaction by a technique which measures the specific activity of the HBr product. At 1 0 C and with the reverse reaction suppressed or irrelevant the values for k/sub H//k/sub T/ are 3.9, 8.2, and 11.6 for X = CH 3 , Cl, and Br, respectively. An isotope effect of 3.5 for X = H was also measured, but the contribution of the reverse reaction was not established. The relatively large isotope effect for X = Br is interpreted in terms of a weakening of the CH bond by neighboring bromine participation. The smaller effect of chlorine may correspond to a minor participation, but the unfavorable inductive effect of the chlorine is also a factor. The case of X = Br is the microscopic reverse of the addition of HBr to 2-methylpropene, and the results are compared with isotope effects in the addition to HBr to olefins. The measurement of isotope effect is, within some described limitations, a convenient and general method for detecting neighboring group participation in hydrogen atom abstractions

  20. Magnetic isotope and magnetic field effects on the DNA synthesis

    Science.gov (United States)

    Buchachenko, Anatoly L.; Orlov, Alexei P.; Kuznetsov, Dmitry A.; Breslavskaya, Natalia N.

    2013-01-01

    Magnetic isotope and magnetic field effects on the rate of DNA synthesis catalysed by polymerases β with isotopic ions 24Mg2+, 25Mg2+ and 26Mg2+ in the catalytic sites were detected. No difference in enzymatic activity was found between polymerases β carrying 24Mg2+ and 26Mg2+ ions with spinless, non-magnetic nuclei 24Mg and 26Mg. However, 25Mg2+ ions with magnetic nucleus 25Mg were shown to suppress enzymatic activity by two to three times with respect to the enzymatic activity of polymerases β with 24Mg2+ and 26Mg2+ ions. Such an isotopic dependence directly indicates that in the DNA synthesis magnetic mass-independent isotope effect functions. Similar effect is exhibited by polymerases β with Zn2+ ions carrying magnetic 67Zn and non-magnetic 64Zn nuclei, respectively. A new, ion–radical mechanism of the DNA synthesis is suggested to explain these effects. Magnetic field dependence of the magnesium-catalysed DNA synthesis is in a perfect agreement with the proposed ion–radical mechanism. It is pointed out that the magnetic isotope and magnetic field effects may be used for medicinal purposes (trans-cranial magnetic treatment of cognitive deceases, cell proliferation, control of the cancer cells, etc). PMID:23851636

  1. Mass independent isotope effects and their observations in nature

    International Nuclear Information System (INIS)

    Thiemens, M.H.

    2002-01-01

    In 1983, Thiemens and Heidenreich reported the first chemically produced mass independent isotope effect. A significant feature of the fractionation was that it identically produced the isotopic relation observed in the calcium-aluminum inclusions in the Allende meteorite. This δ 17 O=δ 18 O composition had previously been thought to represent a nucleosynthetic component as no chemical process was capable of producing a mass independent isotopic composition. It now appears nearly certain that the meteoritic oxygen isotopic anomalies were produced by chemical, rather than nuclear, processes. Since oxygen is the major element in stony planets this represents a major event in the formation of the solar system. In a recent review (Thiemens, 1999), it has been shown that mass independent isotopic compositions are pervasive in the Earth's atmosphere. Molecules which have been demonstrated to possess mass independent isotopic compositions include: O 2 , O 3 , CO 2 , CO, and N 2 O. In each case, the specific nature of the mass independent isotopic composition has provided details of their atmospheric chemistry that could not have been obtained by any other measurement technique. Most recently, solid materials have been observed to possess mass independent isotopic composition. In this paper, these observations are briefly discussed. These solid reservoirs include: 1) carbonates and sulphates from Mars, 2) terrestrial aerosol sulphate, 3) sulphides and sulphates from the Earth, ranging in time from 3.8 to 2.2 billion years before present, 4) sulphates from the Namibian desert and 5) the Antartic Dry Valleys. The information obtained from these measurements is extraordinarily wide ranging, extending from understanding the history of Martian atmosphereregolith interaction to the evolution of the oxygen in the Earth's earliest atmosphere. As was the case for gas phase species, this information and insight could not have been obtained by any other measurement technique

  2. Transport hysteresis and hydrogen isotope effect on confinement

    Science.gov (United States)

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

    2018-03-01

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

  3. Chemical and isotopic evidence for mixing between depleted and enriched mantle, northwestern U.S.A.

    Science.gov (United States)

    Hart, William K.

    1985-01-01

    Combined elemental and Sr, Nd, Pb and O isotopic data for late Cenozoic olivine tholeiite lavas from the northwestern Great Basin indicate derivation from at least two chemically and isotopically distinct mantle source regions with no significant modification by interaction with continental crust. The lack of crustal involvement is a direct reflection of the extensional tectonic environment which favors rapid ascent of magmas, minimal residence time in crustal magma chambers and scattered fissure eruptions. The observed chemical and isotopic variations in the tholeiite suite are attributed to mixing between depleted oceanic type mantle ( 87Sr /86Sr ~ 0.7030 and 143Nd /144Nd ~ 0.51305 ) and old, chemically heterogeneous, isotopically enriched subcontinental mantle ( 87Sr /86Sr ~ 0.7078 and 143Nd /144Nd ~ 0.51233 ). Model incompatible element concentrations suggest strong similarities between the depleted mantle and the mantles beneath normal oceanic ridge segments and back-arc basins and between the enriched mantle and the mantle beneath enriched oceanic ridge segments such as the Azores. Superimposed upon the characteristics derived from the two component mixing model may be the effects of a third mantle source which is identifiable only by its apparent radiogenic 206Pb /204Pb ratios. If present, this third source may reflect a component derived from the downgoing slab of an ancient subduction zone.

  4. Osmium Isotopic Evidence Against an Impact at the Frasnian-Famennian Boundary

    Science.gov (United States)

    Gordon, G. W.; Turekian, K. K.; Rockman, M.; Over, J.

    2007-12-01

    Two sections across the Frasnian-Famennian boundary were analyzed for Re and Os concentrations and 187Os/188Os ratios to evaluate evidence for a meteoritic input coincident with this boundary and its associated mass extinction. These sections are from a siltstone and shale sequence at Irish Gulf in New York, US and a calcareous shale and ferromanganese oxide sequence at La Serre in France. The Irish Gulf section, with an initial 187Os/188Os of ~0.49, does not show the characteristic meteoritic Os imprint with a 187Os/188Os value of about 0.13. Both Re and Os are retained in this section, as indicated by the construction of an isochron with an age of 388 ±41 Ma, consistent with independently determined ages for the Frasnian-Famennian boundary. Although the La Serre section, with Os concentrations as high as 33 ppb and Re concentrations ranging from 1.4 to 7.4 ppb, might be expected to show excellent evidence for a meteoritic contribution, the highly radiogenic isotopic composition (187Os/188Os ranges from 2.42-3.61) instead suggests recent massive Re loss or addition of radiogenic Os. This open system behavior prevents the reconstruction of an initial 187Os/188Os value for the boundary at La Serre. Assuming reasonable Re concentrations prior to loss, however, the Os isotopic value is inconsistent with a large meteoritic component. In addition, this study reinforces the need for Os isotopic evidence, not only enriched PGE concentrations, as substantiation for a meteoritic impact.

  5. Isotopic evidence for the past climates and vegetation of southern Africa

    Directory of Open Access Journals (Sweden)

    J. C. Vogel

    1983-11-01

    Full Text Available The stable isotopes of hydrogen, oxygen and carbon can potentially provide evidence of past climates. The most detailed information has been obtained from variations in the oxygen-18 content of foraminifera from ocean floor cores, the analysis of which has produced a record of ocean temperature changes through the Quaternary and beyond. The use of isotope analysis of continental materials to reveal climatic change is more limited, but some advances have been made in recent years. One approach has been to utilize the variations in the isotopic composition of precipitation as recorded in ancient groundwater. Thus groundwater samples from a confined aquifer on the southern Cape coast show a marked rise in temperature since the Last Glacial maximum. The temperature changes during the Upper Pleistocene and Holocene are also reflected in the oxygen-18 content of stalagmites from the Cango caves in the same region. The widespread occurrence of C4 grasses in the warmer summer rainfall areas of southern Africa provides a novel possibility of observing temporal shifts of climatic boundaries. The distinctly high carbon-13 content of C4 plants is clearly reflected in the skeletons of grazers so that faunal material from suitably situated archaeological sites can be used to observe changes in the composition of the local grass-cover. The evidence thus far accumulated suggests only minor changes since the Upper Pleistocene. The combined evidence to date indicates that temperatures and also precipitation in southern Africa have changed since the Last Glacial maximum, about 18 000 years ago, but that shifts in the boundaries of the various veld-types were probably not very extensive.

  6. Isotopic evidence for the past climates and vegetation of southern Africa

    International Nuclear Information System (INIS)

    Vogel, J.C.

    1983-01-01

    The stable isotopes of hydrogen, oxygen and carbon can potentially provide evidence of past climates. The most detailed information has been obtained from variations in the oxygen-18 content of foraminifera from ocean floor cores, the analysis of which has produced a record of ocean temperature changes through the Quaternary and beyond. The use of isotope analysis of continental materials to reveal climatic change is more limited, but some advances have been made in recent years. One approach has been to utilize the variations in the isotopic composition of precipitation as recorded in ancient groundwater. Thus groundwater samples from a confined aquifer on the southern Cape coast show a marked rise in temperature since the Last Glacial maximum. The temperature changes during the Upper Pleistocene and Holocene are also reflected in the oxygen-18 content of stalagmites from the Cango caves in the same region. The widespread occurrence of C 4 grasses in the warmer summer rainfall areas of southern Africa provides a novel possibility of observing temporal shifts of climatic boundaries. The distinctly high carbon-13 content of C 4 plants is clearly reflected in the skeletons of grazers so that faunal material from suitably situated archaeological sites can be used to observe changes in the composition of the local grass-cover. The evidence thus far accumulated suggests only minor changes since the Upper Pleistocene. The combined evidence to date indicates that temperatures and also precipitation in southern Africa have changed since the Last Glacial maximum, about 18 000 years ago, but that shifts in the boundaries of the various veld-types were probably not very extensive

  7. Isotope and mixture effects on neoclassical transport in the pedestal

    Science.gov (United States)

    Pusztai, Istvan; Buller, Stefan; Omotani, John T.; Newton, Sarah L.

    2017-10-01

    The isotope mass scaling of the energy confinement time in tokamak plasmas differs from gyro-Bohm estimates, with implications for the extrapolation from current experiments to D-T reactors. Differences in mass scaling in L-mode and various H-mode regimes suggest that the isotope effect may originate from the pedestal. In the pedestal, sharp gradients render local diffusive estimates invalid, and global effects due to orbit-width scale profile variations have to be taken into account. We calculate neoclassical cross-field fluxes from a radially global drift-kinetic equation using the PERFECT code, to study isotope composition effects in density pedestals. The relative reduction to the peak heat flux due to global effects as a function of the density scale length is found to saturate at an isotope-dependent value that is larger for heavier ions. We also consider D-T and H-D mixtures with a focus on isotope separation. The ability to reproduce the mixture results via single-species simulations with artificial ``DT'' and ``HD'' species has been considered. These computationally convenient single ion simulations give a good estimate of the total ion heat flux in corresponding mixtures. Funding received from the International Career Grant of Vetenskapsradet (VR) (330-2014-6313) with Marie Sklodowska Curie Actions, Cofund, Project INCA 600398, and Framework Grant for Strategic Energy Research of VR (2014-5392).

  8. Stable isotope and DNA evidence for ritual sequences in Inca child sacrifice

    Science.gov (United States)

    Wilson, Andrew S.; Taylor, Timothy; Ceruti, Maria Constanza; Chavez, Jose Antonio; Reinhard, Johan; Grimes, Vaughan; Meier-Augenstein, Wolfram; Cartmell, Larry; Stern, Ben; Richards, Michael P.; Worobey, Michael; Barnes, Ian; Gilbert, M. Thomas P.

    2007-01-01

    Four recently discovered frozen child mummies from two of the highest peaks in the south central Andes now yield tantalizing evidence of the preparatory stages leading to Inca ritual killing as represented by the unique capacocha rite. Our interdisciplinary study examined hair from the mummies to obtain detailed genetic and diachronic isotopic information. This approach has allowed us to reconstruct aspects of individual identity and diet, make inferences concerning social background, and gain insight on the hitherto unknown processes by which victims were selected, elevated in social status, prepared for a high-altitude pilgrimage, and killed. Such direct information amplifies, yet also partly contrasts with, Spanish historical accounts. PMID:17923675

  9. Inverse iron isotope effect on the transition temperature of the (Ba,K)Fe2As2 superconductor.

    Science.gov (United States)

    Shirage, Parasharam M; Kihou, Kunihiro; Miyazawa, Kiichi; Lee, Chul-Ho; Kito, Hijiri; Eisaki, Hiroshi; Yanagisawa, Takashi; Tanaka, Yasumoto; Iyo, Akira

    2009-12-18

    We report that the (Ba,K)Fe(2)As(2) superconductor (transition temperature, T(c) approximately 38 K) has an inverse iron isotope coefficient alpha(Fe) = -0.18(3) (where T(c) approximately M(-alphaFe) and M is the iron isotope mass); i.e., the sample containing the large iron isotope mass depicts a higher T(c). Systematic inverse shifts in T(c) were clearly observed between the samples using three types of Fe isotopes ((54)Fe, natural Fe, and (57)Fe). This indicates the first evidence of the inverse isotope effect in high-T(c) superconductors. This anomalous mass dependence on T(c) implies an exotic coupling mechanism in Fe-based superconductors.

  10. HPLC isotope effects and macrocycles: the case of Echinocandin B

    International Nuclear Information System (INIS)

    Jones, A.N.; Simpson, R.E.; Jenkins, H.J.

    1992-01-01

    Echinocandin B was catalytically reduced with hydrogen, deuterium, or tritium. HPLC analysis of the products showed that the labeled analogs exhibited a significant isotope effect relative to the unlabeled parent, with the elution order tritiated < deuterated < hydrogenated. Mass spectral data and specific activity measurements indicated label incorporation exceeded saturation of the double bonds. Proton nmr of the deuterated compound indicated labeling was confined to the aliphatic side chain. A model compound, anilonosteareamide, prepared from the linoleic precursor by reduction with hydrogen or deuterium, incorporated the label only in the aliphatic chain, and also exhibited an isotope effect. This helped confirm that label incorporation in only the fatty acid portion of tetrahydroechinocandin B was sufficient to cause the observed isotope effect. (Author)

  11. Uranium Isotope Compositions of Mid-Proterozoic Organic-rich Mudrocks: Evidence for an Episode of Increased Ocean Oxygenation at ca. 1.36 Ga and Evaluation of the Effect of Post-Depositional Hydrothermal Fluid Flow

    Science.gov (United States)

    Kendall, B.; Yang, S.; Lu, X.; Zhang, F.; Zheng, W.

    2016-12-01

    The U isotope system represents a relatively new paleoredox proxy that can help trace the evolution of global ocean redox chemistry, but has rarely been applied to the Mid-Proterozoic. We report U isotope data for marine black shales of the early Mesoproterozoic Velkerri Formation (Roper Group) and late Paleoproterozoic Wollogorang Formation (Tawallah Group) from the McArthur Basin, Northern Australia. An average authigenic δ238U of 0.13 ± 0.04‰ (1SD; relative to standard CRM145) was obtained for six euxinic shales from a 1 m interval that previously yielded a precise Re-Os depositional age of 1361 ± 21 Ma. After correcting for a U isotope fractionation of 0.60-0.85‰ between seawater and open-ocean euxinic sediments, we infer that coeval global seawater had a δ238U of -0.47‰ to -0.72‰, which is 0.1-0.3‰ lighter than modern seawater (-0.40 ± 0.03‰). A U isotope mass-balance model suggests that anoxic marine environments accounted for 25-50% of the global oceanic U sink at 1.36 Ga, which is 3-7 times greater than today. The model suggests that a significant proportion, potentially even a majority, of the seafloor was not covered by anoxic waters. Hence, we infer that a significant extent of the ocean floor was covered by O2-bearing waters at 1.36 Ga. The O2 concentrations of those waters were not necessarily high, and a large expanse of weakly to mildly oxygenated deep waters is consistent with the U isotope data. Uranium isotope data from a 1 m interval in the lower Velkerri Formation, deposited at 1417 ± 29 Ma based on Re-Os geochronology, yield a greater estimate for the extent of ocean anoxia. Hence, the upper Velkerri Formation may capture a transient episode of increased ocean oxygenation. Previous Re-Os isotope data from black shales of the ca. 1.73 Ga Paleoproterozoic Wollogorang Formation yielded an erroneously young date of 1359 ± 150 Ma because hydrothermal fluids percolated through the Tawallah Group rocks at ca. 1640 Ma. Higher δ238U

  12. Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

    DEFF Research Database (Denmark)

    Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

    2012-01-01

    -labeled water and 18O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed......In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and “Aromatoleum aromaticum strain EbN1” were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. 18O...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  13. Quantum instanton evaluation of the kinetic isotope effects

    Energy Technology Data Exchange (ETDEWEB)

    Vanicek, Jiri; Miller, William H.; Castillo, Jesus F.; Aoiz, F.Javier

    2005-04-19

    A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum instanton approximation for the rate constant and on the path integral Metropolis Monte-Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method is more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single reaction path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte-Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H+H{sub 2} {yields} H{sub 2}+H. In all seven test cases, for temperatures between 250 K and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than {approx}10%.

  14. Intrapopulation variability shaping isotope discrimination and turnover: experimental evidence in arctic foxes.

    Directory of Open Access Journals (Sweden)

    Nicolas Lecomte

    Full Text Available Tissue-specific stable isotope signatures can provide insights into the trophic ecology of consumers and their roles in food webs. Two parameters are central for making valid inferences based on stable isotopes, isotopic discrimination (difference in isotopic ratio between consumer and its diet and turnover time (renewal process of molecules in a given tissue usually measured when half of the tissue composition has changed. We investigated simultaneously the effects of age, sex, and diet types on the variation of discrimination and half-life in nitrogen and carbon stable isotopes (δ¹⁵N and δ¹³C, respectively in five tissues (blood cells, plasma, muscle, liver, nail, and hair of a top predator, the arctic fox Vulpes lagopus.We fed 40 farmed foxes (equal numbers of adults and yearlings of both sexes with diet capturing the range of resources used by their wild counterparts. We found that, for a single species, six tissues, and three diet types, the range of discrimination values can be almost as large as what is known at the scale of the whole mammalian or avian class. Discrimination varied depending on sex, age, tissue, and diet types, ranging from 0.3‰ to 5.3‰ (mean  = 2.6‰ for δ¹⁵N and from 0.2‰ to 2.9‰ (mean  = 0.9‰ for δ¹³C. We also found an impact of population structure on δ¹⁵N half-life in blood cells. Varying across individuals, δ¹⁵N half-life in plasma (6 to 10 days was also shorter than for δ¹³C (14 to 22 days, though δ¹⁵N and δ¹³C half-lives are usually considered as equal.Overall, our multi-factorial experiment revealed that at least six levels of isotopic variations could co-occur in the same population. Our experimental analysis provides a framework for quantifying multiple sources of variation in isotopic discrimination and half-life that needs to be taken into account when designing and analysing ecological field studies.

  15. Isotopic effects on non-linearity, molecular radius and intermolecular ...

    Indian Academy of Sciences (India)

    study the isotopic effects on the non-linearity parameter and the physicochemical proper- ties of the liquids, which in turn has been used to study their effect on the intermolecular interactions produced thereof. Keywords. Non-linearity parameter; molecular radius; free length; intermolecular inter- actions. PACS Nos 43.25.

  16. Stable isotope methods: The effect of gut contents on isotopic ratios of zooplankton

    Science.gov (United States)

    Hill, J. M.; McQuaid, C. D.

    2011-05-01

    In the past decade there has been an increased awareness of the potential for methodological bias resulting from multiple pre-analytical procedures in foodweb interpretations based on stable isotope techniques. In the case of small organisms, this includes the effect of gut contents on whole body signatures. Although gut contents may not reflect actual assimilation, their carbon and nitrogen values will be isotopically lighter than after the same material has been assimilated. The potential skewing of isotopic ratios in whole organism samples is especially important for aquatic environments as many studies involve trophic relationships among small zooplankton. This is particularly important in pelagic waters, where herbivorous zooplankton comprise small taxa. Hence this study investigated the effect of gut contents on the δ13C and δ15N ratios of three size classes of zooplankton (1.0-2.0, 2.0-4.0 and >4.0 mm) collected using bongo net tows in the tropical waters of the south-west Indian Ocean. Animals were collected at night, when they were likely to be feeding, sieved into size classes and separated into genera. We focused on Euphausia spp which dominated zooplankton biomass. Three treatment types were processed: bulk animals, bulk animals without guts and tail muscle from each size class at 10 bongo stations. The δ15N ratios were influenced by zooplankton size class, presumably reflecting ontogenetic changes in diet. ANOVA post hoc results and correlations in δ15N signatures among treatments suggest that gut contents may not affect overall nitrogen signatures of Euphausia spp., but that δ13C signatures may be significantly altered by their presence. Carbon interpretations however, were complicated by potential effects of variation in chitin, lipids and metabolism among tissues and the possibility of opportunistic omnivory. Consequently we advocate gut evacuation before sacrifice in euphausiids if specific tissue dissection is impractical and recommend

  17. Low temperature isotope effects of hydrogen diffusion in metallic glasses

    International Nuclear Information System (INIS)

    Hofmann, A.; Kronmueller, H.

    1989-01-01

    Snoek-like relaxation peaks of Hydrogen and Deuterium in amorphous Fe 80 B 20 , Fe 40 Ni 40 P 14 B 6 and Fe 91 Zr 9 are detected. At low H, D concentrations the peaks are near 200 K and show small isotope effects of the average activation energies (anti Q H ≅ 0.6 eV, anti Q D - anti Q H ≤ 10 meV). For higher H, D-contents the peaks shift to lower temperatures around to 120 K and show distinct isotope effects in the activation energies (anti Q H ≅ 0.3 eV, anti Q D - anti Q H ≅ 30 meV) and in the amplitude of the low temperature tails of the relaxation peaks. This points to isotope mass dependent deviations from the Arrhenius law due to nonthermal tunneling processes. (orig.)

  18. Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

    International Nuclear Information System (INIS)

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

    1998-01-01

    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  19. The evidence for Allee effects

    Science.gov (United States)

    Andrew M. Kramer; Brian Dennis; Andrew M. Liebhold; John M. Drake

    2009-01-01

    Allee effects are an important dynamic phenomenon believed to be manifested in several population processes, notably extinction and invasion. Though widely cited in these contexts, the evidence for their strength and prevalence has not been critically evaluated. We review results from 91 studies on Allee effects in natural animal populations. We focus on empirical...

  20. Identifying vital effects in Halimeda algae with Ca isotopes

    Directory of Open Access Journals (Sweden)

    C. L. Blättler

    2014-12-01

    Full Text Available Geochemical records of biogenic carbonates provide some of the most valuable records of the geological past, but are often difficult to interpret without a mechanistic understanding of growth processes. In this experimental study, Halimeda algae are used as a test organism to untangle some of the specific factors that influence their skeletal composition, in particular their Ca-isotope composition. Algae were stimulated to precipitate both calcite and aragonite by growth in artificial Cretaceous seawater, resulting in experimental samples with somewhat malformed skeletons. The Ca-isotope fractionation of the algal calcite (−0.6‰ appears to be much smaller than that for the algal aragonite (−1.4‰, similar to the behaviour observed in inorganic precipitates. However, the carbonate from Halimeda has higher Ca-isotope ratios than inorganic forms by approximately 0.25‰, likely because of Rayleigh distillation within the algal intercellular space. In identifying specific vital effects and the magnitude of their influence on Ca-isotope ratios, this study suggests that mineralogy has a first-order control on the marine Ca-isotope cycle.

  1. Textural and Isotopic Evidence for Silica Cementation in 1.88 GA Granular Iron Formation

    Science.gov (United States)

    Brengman, L. A.; Fedo, C.; Martin, W.

    2016-12-01

    Controls on quartz precipitation mechanisms and silicon isotope fractionation during diagenesis of Precambrian iron formation (IF) are not well constrained. The goal of this study is to identify textural evidence for the relative timing of silica cementation of granular units from the near un-metamorphosed 1.88 Ga Biwabik IF and determine the silicon isotope composition for such a silicification event. The lowermost IF (lower cherty, LC) consists of granular units associated with high-energy sedimentary structures interpreted to represent shallow-marine shelf deposition. Up-section is marked by an abrupt shift to banded units interpreted as a transition to quiescent (deeper) water, followed by a return to granular textures and shallower conditions (upper cherty, UC). We first surveyed granular samples of the lower stromatolitic (LC) and upper oncolitic facies (UC) to identify sedimentary textures and cement. LC units consist of microquartz (chert), megaquartz, hematite, carbonate, and detrital quartz, chert, and quartz/Fe-oxide intraclastic material. In UC samples, space between granular material (hematite, magnetite, quartz ooids/intraclasts) is filled by mega-quartz cement, and cross-cutting mega-quartz veins. We targeted mega-quartz cement, and veins for δ30Si analysis via secondary ion mass spectrometry. The average measured δ30Si value of cement (δ30Siavg. cement UC6b = -3.11 ± 0.21 ‰) is significantly different than associated veins (δ30Siavg. vein UC6b = 0.21 ± 0.21 ‰; δ30Siavg. vein LC4 = 0.39 ± 0.21 ‰), both within and between samples. We interpret the relative difference between cement and veins to represent quartz precipitation under different geochemical conditions, and therefore at different times. Combining isotopic and textural evidence, we interpret silica cementation to pre-date veins, and represent quartz precipitation that either varied in rate, or occurred under closed-system conditions affected by Rayleigh distillation. Both

  2. Magic numbers and isotopic effect of ion clusters

    International Nuclear Information System (INIS)

    Wang Guanghou

    1989-04-01

    The magic numbers and isotopic effect as well as stable configurations in relation to the charge state of the clusters are discussed. Ionic (atomic) clusters are small atomic aggregates, a physical state between gas and solid states, and have many interesting properties, some of them are more or less similar to those in nuclei

  3. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a-Deuterium kinetic isotope effects (KIE's) have been determined for the reaction of methyl iodide with a series of reducing agents. Reagents which transfer hydride ion in an SN2 reaction show small inverse or small normal KIE's. Reagents which transfer an electron to methyl iodide to produce...

  4. Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

    The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

  5. Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology

    Directory of Open Access Journals (Sweden)

    Nicholas E.C. Fleming

    2015-07-01

    Full Text Available Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and δ13C and δ15N stable isotope values, we examined: (1 whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2 Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3 When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in δ15N (trophic position were evident between all three species, with size-based and temporal shifts in δ15N apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous

  6. No evidence of reduced collectivity in Coulomb-excited Sn isotopes

    Science.gov (United States)

    Kumar, R.; Saxena, M.; Doornenbal, P.; Jhingan, A.; Banerjee, A.; Bhowmik, R. K.; Dutt, S.; Garg, R.; Joshi, C.; Mishra, V.; Napiorkowski, P. J.; Prajapati, S.; Söderström, P.-A.; Kumar, N.; Wollersheim, H.-J.

    2017-11-01

    In a series of Coulomb excitation experiments the first excited 2+ states in semimagic Sn 112 ,116 ,118 ,120 ,122 ,124 isotopes were excited using a 58Ni beam at safe Coulomb energy. The B (E 2 ; 0+→2+) values were determined with high precision (˜3 %) relative to 58Ni projectile excitation. These results disagree with previously reported B (E 2 ↑) values [A. Jungclaus et al., Phys. Lett. B 695, 110 (2011)., 10.1016/j.physletb.2010.11.012] extracted from Doppler-shift attenuation lifetime measurements, whereas the reported mass dependence of B (E 2 ↑) values is very similar to a recent Coulomb excitation study [J. M. Allmond et al., Phys. Rev. C 92, 041303(R) (2015), 10.1103/PhysRevC.92.041303]. The stable Sn isotopes, key nuclei in nuclear structure, show no evidence of reduced collectivity and we, thus, reconfirm the nonsymmetric behavior of reduced transition probabilities with respect to the midshell A =116 .

  7. Identification of Groundwater Nitrate Contamination from Explosives Used in Road Construction: Isotopic, Chemical, and Hydrologic Evidence.

    Science.gov (United States)

    Degnan, James R; Böhlke, J K; Pelham, Krystle; Langlais, David M; Walsh, Gregory J

    2016-01-19

    Explosives used in construction have been implicated as sources of NO3(-) contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO3(-) can be complicated by other NO3(-) sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO3(-) transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO3(-) sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO3(-) (low δ(15)N, high δ(18)O) from dissolution of unexploded NH4NO3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO3(-) subjected to partial denitrification (high δ(15)N, high δ(18)O); (3) relatively persistent concentrations of blasting-related biogenic NO3(-) derived from nitrification of NH4(+) (low δ(15)N, low δ(18)O); and (4) stable but spatially variable biogenic NO3(-) concentrations, consistent with recharge from septic systems (high δ(15)N, low δ(18)O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N2) and isotopic fractionation trends associated with denitrification (Δδ(15)N/Δδ(18)O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

  8. Menopause effect on blood Fe and Cu isotope compositions.

    Science.gov (United States)

    Jaouen, Klervia; Balter, Vincent

    2014-02-01

    Iron (δ(56) Fe) and copper (δ(65) Cu) stable isotope compositions in blood of adult human include a sex effect, which still awaits a biological explanation. Here, we investigate the effect of menopause by measuring blood δ(56) Fe and δ(65) Cu values of aging men and women. The results show that, while the Fe and Cu isotope compositions of blood of men are steady throughout their lifetime, postmenopausal women exhibit blood δ(65) Cu values similar to men, and δ(56) Fe values intermediate between men and premenopausal women. The residence time of Cu and Fe in the body likely explains why the blood δ(65) Cu values, but not the δ(56) Fe values, of postmenopausal women resemble that of men. We suggest that the Cu and Fe isotopic fractionation between blood and liver resides in the redox reaction occurring during hepatic solicitation of Fe stores. This reaction affects the Cu speciation, which explains why blood Cu isotope composition is impacted by the cessation of menstruations. Considering that Fe and Cu sex differences are recorded in bones, we believe this work has important implications for their use as a proxy of sex or age at menopause in past populations. Copyright © 2013 Wiley Periodicals, Inc.

  9. Tritium conductivity and isotope effect in proton-conducting perovskites

    International Nuclear Information System (INIS)

    Mukundan, R.; Brosha, E.L.; Birdsell, S.A.; Costello, A.L.; Garzon, F.H.; Willms, R.S.

    1999-01-01

    The tritium ion conductivities of SrZr 0.9 Yb 0.1 O 2.95 and BaCe 0.9 Yb 0.1 O 2.95 have been measured by ac impedance analysis. The high tritium conductivity of these perovskites could potentially lead to their application as an electrochemical membrane for the recovery of tritium from tritiated gas streams. The conductivities of these perovskites, along with SrCe 0.95 Yb 0.05 O 2.975 , were also measured in hydrogen- and deuterium-containing atmospheres to illustrate the isotope effect. For the strontium zirconate and barium cerate samples, the impedance plot consists of two clearly resolved arcs, a bulk and a grain boundary arc, in the temperature range 50--350 C. However, for the strontium cerate sample, the clear resolution of the bulk conductivity was not possible and only the total conductivity was measurable. Thus, the isotope effect was clearly established only for the strontium zirconate and barium cerate samples. The decrease in bulk conductivity with increasing isotope mass was found to be a result of an increase in the activation energy for conduction accompanied by a decrease in the pre-exponential factor. Since the concentration of the mobile species (H+, D+, or T+) should remain relatively constant at T < 350 C, this increase in activation energy is directly attributable to the increased activation energy for the isotope mobility

  10. Rb-Sr, Sm-Nd, K-Ca, O, and H isotopic study of Cretaceous-Tertiary boundary sediments, Caravaca, Spain Evidence for an oceanic impact site

    Science.gov (United States)

    Depaolo, D. J.; Kyte, F. T.; Marshall, B. D.; Oneil, J. R.; Smit, J.

    1983-01-01

    The results of isotopic and trace-element-abundance analyses of Ir-enriched Cretaceous-Tertiary-boundary clay sediments from Caravaca, Spain, and of adjacent carbonate and marl layers, are presented. Acetic-acid and HCl leachates and residues were analyzed by isotope dilution to determine K, Rb, Sr, Sm, and Nd concentrations and Sr-87/Sr-86 and Nd-143/Nd-144 ratios. The stable isotope ratios delta-D, delta-(C-13), and delta-(0-18) were also determined. The results are presented in tables and graphs and compared with published data on the Caravaca sediments and on samples from other locations. The boundary clay is found to be distinguished from the adjacent layers by its isotopic ratios and to be of mainly terrestrial, lithospheric (deeper than 3-km) origin. Although submarine-weathering effects are evident and difficult to quantify, the degree of variation in Ni, Ir, Sr, and REE concentrations is considered too large to be attributed to postdepositional processes alone. These findings are seen as evidence for the ocean impact of a large single asteroid producing a worldwide blanket of ejecta, a large injection of water vapor into the atmosphere, and perhaps a gigantic tsunami, at the end of the Cretaceous period.

  11. Stable Isotopes and Zooarchaeology at Teotihuacan, Mexico Reveal Earliest Evidence of Wild Carnivore Management in Mesoamerica.

    Science.gov (United States)

    Sugiyama, Nawa; Somerville, Andrew D; Schoeninger, Margaret J

    2015-01-01

    From Roman gladiatorial combat to Egyptian animal mummies, the capture and manipulation of carnivores was instrumental in helping to shape social hierarchies throughout the ancient world. This paper investigates the historical inflection point when humans began to control animals not only as alimental resources but as ritual symbols and social actors in the New World. At Teotihuacan (A.D. 1-550), one of the largest pre-Hispanic cities, animal remains were integral components of ritual caches expressing state ideology and militarism during the construction of the Moon and the Sun Pyramids. The caches contain the remains of nearly 200 carnivorous animals, human sacrificial victims and other symbolic artifacts. This paper argues the presence of skeletal pathologies of infectious disease and injuries manifest on the carnivore remains show direct evidence of captivity. Stable isotope analysis (δ13C and δ15N) of bones and teeth confirms that some of these carnivores were consuming high levels of C4 foods, likely reflecting a maize-based anthropocentric food chain. These results push back the antiquity of keeping captive carnivores for ritualistic purposes nearly 1000 years before the Spanish conquistadors described Moctezuma's zoo at the Aztec capital. Mirroring these documents the results indicate a select group of carnivores at Teotihuacan may have been fed maize-eating omnivores, such as dogs and humans. Unlike historical records, the present study provides the earliest and direct archaeological evidence for this practice in Mesoamerica. It also represents the first systematic isotopic exploration of a population of archaeological eagles (n = 24) and felids (n = 29).

  12. Stable Isotopes and Zooarchaeology at Teotihuacan, Mexico Reveal Earliest Evidence of Wild Carnivore Management in Mesoamerica.

    Directory of Open Access Journals (Sweden)

    Nawa Sugiyama

    Full Text Available From Roman gladiatorial combat to Egyptian animal mummies, the capture and manipulation of carnivores was instrumental in helping to shape social hierarchies throughout the ancient world. This paper investigates the historical inflection point when humans began to control animals not only as alimental resources but as ritual symbols and social actors in the New World. At Teotihuacan (A.D. 1-550, one of the largest pre-Hispanic cities, animal remains were integral components of ritual caches expressing state ideology and militarism during the construction of the Moon and the Sun Pyramids. The caches contain the remains of nearly 200 carnivorous animals, human sacrificial victims and other symbolic artifacts. This paper argues the presence of skeletal pathologies of infectious disease and injuries manifest on the carnivore remains show direct evidence of captivity. Stable isotope analysis (δ13C and δ15N of bones and teeth confirms that some of these carnivores were consuming high levels of C4 foods, likely reflecting a maize-based anthropocentric food chain. These results push back the antiquity of keeping captive carnivores for ritualistic purposes nearly 1000 years before the Spanish conquistadors described Moctezuma's zoo at the Aztec capital. Mirroring these documents the results indicate a select group of carnivores at Teotihuacan may have been fed maize-eating omnivores, such as dogs and humans. Unlike historical records, the present study provides the earliest and direct archaeological evidence for this practice in Mesoamerica. It also represents the first systematic isotopic exploration of a population of archaeological eagles (n = 24 and felids (n = 29.

  13. Stable Isotopes and Zooarchaeology at Teotihuacan, Mexico Reveal Earliest Evidence of Wild Carnivore Management in Mesoamerica

    Science.gov (United States)

    Sugiyama, Nawa; Somerville, Andrew D.; Schoeninger, Margaret J.

    2015-01-01

    From Roman gladiatorial combat to Egyptian animal mummies, the capture and manipulation of carnivores was instrumental in helping to shape social hierarchies throughout the ancient world. This paper investigates the historical inflection point when humans began to control animals not only as alimental resources but as ritual symbols and social actors in the New World. At Teotihuacan (A.D. 1–550), one of the largest pre-Hispanic cities, animal remains were integral components of ritual caches expressing state ideology and militarism during the construction of the Moon and the Sun Pyramids. The caches contain the remains of nearly 200 carnivorous animals, human sacrificial victims and other symbolic artifacts. This paper argues the presence of skeletal pathologies of infectious disease and injuries manifest on the carnivore remains show direct evidence of captivity. Stable isotope analysis (δ13C and δ15N) of bones and teeth confirms that some of these carnivores were consuming high levels of C4 foods, likely reflecting a maize-based anthropocentric food chain. These results push back the antiquity of keeping captive carnivores for ritualistic purposes nearly 1000 years before the Spanish conquistadors described Moctezuma’s zoo at the Aztec capital. Mirroring these documents the results indicate a select group of carnivores at Teotihuacan may have been fed maize-eating omnivores, such as dogs and humans. Unlike historical records, the present study provides the earliest and direct archaeological evidence for this practice in Mesoamerica. It also represents the first systematic isotopic exploration of a population of archaeological eagles (n = 24) and felids (n = 29). PMID:26332042

  14. Isotope effects in photo dissociation of ozone with visible light

    Science.gov (United States)

    Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

    2014-05-01

    Ozone (O3) plays a key role for many chemical oxidation processes in the Earth's atmosphere. In these chemical reactions, ozone can transfer oxygen to other trace gases. This is particularly interesting, since O3 has a very peculiar isotope composition. Following the mass dependent fractionation equation δ17O = 0.52 * δ18O, most fractionation processes depend directly on mass. However, O3 shows an offset to the mass dependent fractionation line. Processes, which show such anomalies, are termed mass independent fractionations (MIF). A very well studied example for a chemical reaction that leads to mass independent fractionation is the O3 formation reaction. To what degree O3 destruction reactions need to be considered in order to understand the isotope composition of atmospheric O3 is still not fully understood and an open question within scientific community. We set up new experiments to investigate the isotope effect resulting from photo dissociation of O3 in the Chappuis band (R1). Initial O3 is produced by an electric discharge. After photolysis O3 is collected in a cold trap at the triple point temperature of nitrogen (63K). O3 is then converted to O2 in order to measure the oxygen isotopes of O3 using isotope ratio mass spectrometry. To isolate O3 photo dissociation (R1) from O3 decomposition (R2) and secondary O3 formation (R3), we use varying amounts of carbon monoxide (CO) as O atom quencher (R4). In this way we suppress the O + O3 reaction (R3) and determine the isotope fractionation in R1 and R2 separately. We present first results on the isotope effects in O3 photo dissociation with visible light in the presence of different bath gases. Results are interpreted based on chemical kinetics modeling. (R1) O3 + hυ → O (3P) + O2 (R2) O3 + O (3P) → 2 O2 (R3) O + O2 + M → O3 + M (R4) O (3P) + CO + M → CO2 + M

  15. Stable Isotope Signatures of Middle Palaeozoic Ahermatypic Rugose Corals – Deciphering Secondary Alteration, Vital Fractionation Effects, and Palaeoecological Implications

    Science.gov (United States)

    Jakubowicz, Michal; Berkowski, Blazej; López Correa, Matthias; Jarochowska, Emilia; Joachimski, Michael; Belka, Zdzislaw

    2015-01-01

    This study investigates stable isotope signatures of five species of Silurian and Devonian deep-water, ahermatypic rugose corals, providing new insights into isotopic fractionation effects exhibited by Palaeozoic rugosans, and possible role of diagenetic processes in modifying their original isotopic signals. To minimize the influence of intraskeletal cements on the observed signatures, the analysed specimens included unusual species either devoid of large intraskeletal open spaces ('button corals': Microcyclus, Palaeocyclus), or typified by particularly thick corallite walls (Calceola). The corals were collected at four localities in the Holy Cross Mountains (Poland), Mader Basin (Morocco) and on Gotland (Sweden), representing distinct diagenetic histories and different styles of diagenetic alteration. To evaluate the resistance of the corallites to diagenesis, we applied various microscopic and trace element preservation tests. Distinct differences between isotopic compositions of the least-altered and most-altered skeleton portions emphasise a critical role of material selection for geochemical studies of Palaeozoic corals. The least-altered parts of the specimens show marine or near-marine stable isotope signals and lack positive correlation between δ13C and δ18O. In terms of isotopic fractionation mechanisms, Palaeozoic rugosans must have differed considerably from modern deep-water scleractinians, typified by significant depletion in both 18O and 13C, and pronounced δ13C-δ18O co-variance. The fractionation effects exhibited by rugosans seem similar rather to the minor isotopic effects typical of modern non-scleractinian corals (octocorals and hydrocorals). The results of the present study add to growing evidence for significant differences between Scleractinia and Rugosa, and agree with recent studies indicating that calcification mechanisms developed independently in these two groups of cnidarians. Consequently, particular caution is needed in using

  16. Studies on fractionation of ytterbium isotopes in Yb(III)-acetate/Yb-amalgam system. Even-odd effect

    Energy Technology Data Exchange (ETDEWEB)

    Dembinski, W.; Poninski, M.; Fiedler, R.

    1997-12-31

    The fractionation of ytterbium isotopes with the even and odd numbers of neutrons was investigated in a Yb(III)-acetate/Yb-amalgam exchange systems. The light isotope was preferentially fractionated to the amalgam phase. The values of the unit separation gain per mass difference,{epsilon}, were found to be -0.00054 for {sup 176/171}Yb and -0.00069 for {sup 176/174}Yb The difference which amounted to 0.00015 is an evidence for the occurrence of the so called `even-odd` effect. It was also found that the chemical isotope shift of ytterbium was monitored by optical isotope shift its atomic spectra. (author). 23 refs, 7 figs, 4 tabs.

  17. Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.; Kasprzyk, G.; Gumolka, L.; Staedter, W.

    1993-01-01

    The 13 C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphoric acids (PA) and by 85% H 3 PO 4 has been studied in the temperature interval of 60-150 deg C. The values of the 13 C (1) isotope effects in the decarbonylation of lactic acid in 100% H 3 PO 4 , in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C (1)- OH bond is broken in the rate-controlling step of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90-130 deg C the experimental 13 C fractionation factors determined in concentrated PA approach quite closely the 13 C fractionation corresponding to C (2)- C (1) bond scission. The 13 C (1) kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110-150 deg C coincide with the 13 C isotope effects calculated assuming that the frequency corresponding to the C (1) -OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H 3 PO 4 has been suggested. A possible secondary 18 O and a primary 18 O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too. (author) 21 refs.; 3 tabs

  18. Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

    International Nuclear Information System (INIS)

    Mango, Helen; Ryan, Peter

    2015-01-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ 34 S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in 34 S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ 34 S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ 34 S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ 34 S = – 5.2 to 63‰ with higher 34 S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ 34 S

  19. Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

    Energy Technology Data Exchange (ETDEWEB)

    Mango, Helen, E-mail: helen.mango@castleton.edu [Department of Natural Sciences, Castleton State College, 233 South Street, Castleton, VT 05735 (United States); Ryan, Peter, E-mail: pryan@middlebury.edu [Department of Geology, Middlebury College, 276 Bicentennial Way, Middlebury, VT 05753 (United States)

    2015-02-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ{sup 34}S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in {sup 34}S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ{sup 34}S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ{sup 34}S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ{sup 34}S = – 5.2 to 63‰ with higher {sup 34}S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ{sup 34}S.

  20. The oxygen isotope composition of earth's oldest rocks and evidence of a terrestrial magma ocean

    DEFF Research Database (Denmark)

    Rumble, D.; Bowring, S.; Iizuka, T.

    2013-01-01

    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact...

  1. Aerodynamic effects in isotope separation by gaseous diffusion

    International Nuclear Information System (INIS)

    Bert, L.A.; Prosperetti, A.; Fiocchi, R.

    1978-01-01

    The turbulent flow of an isotopic mixture in a porous-walled pipe is considered in the presence of suction through the wall. A simple model is formulated for the evaluation of aerodynamic effects on the separation efficiency. The predictions of the model are found to compare very favourably with experiment. In the limit of small suction velocities, results obtained by other investigators for diffusion in a turbulent steam are recovered. (author)

  2. Isotope effect in thermodynamic parameters of styrene polymerization

    International Nuclear Information System (INIS)

    Lebedev, B.V.; Lebedev, N.K.; Smirnova, N.N.

    1985-01-01

    Isotope effects in the enthalpy, entropy and Gibbs energy of the styrene polymerization process are detected by adiabatic- and isothermal calorimetry methods. Thermodynamic parameters of styrene- and deuterostyrene polymerization are calculated in the range from 0 to 350 K. Differences in thermodynamic quantities of these processes are explained by the influence of hydrogen substitution by deuterium and constitute: for enthalpy and Gibbs energy 2-3 kJ/mol, for entropy - 2-3 J/(mol x k)

  3. Is the isotope effect a consequence of magnetic transport?

    International Nuclear Information System (INIS)

    Zurro, B.; Rodriguez-Rodrigo, L.; Castejon, F.

    1994-01-01

    The isotope effect, i.e. the improved confinement of deuterium fuelling compared with hydrogen fuelling, shows up in nearly all tokamaks with various type of wall conditioning and in various confinement regimes. Many empirical scalings for energy confinement include a dependence of the energy replacement time τ E ∝ A i α where α ∼ 1/2, and A i is the atomic mass of the plasma ion species. However, no convincing theoretical justification has so far been found for such a dependence; classical transport would lead us to expect α 1/2, as would some theories for anomalous transport (e.g. those based on drift wave turbulence). This empirical scaling effect has been reviewed along with other relevant theories in a recent paper. The main conclusion drawn therein was that this effect was an unsolved fundamental problem in tokamak transport theory. In this paper, we put forward the hypothesis that the isotope effect is a consequence of magnetic transport in the plasma which we can support by observed reductions in the magnetic turbulence level in deuterium operated plasmas. The proposition is supported by data which we claim give some information about the level of stochastic magnetic turbulence within the plasma. These data show a reduction for the deuterium in the difference between the apparent temperature of a central ion (C V) and that of the main ion, hydrogen or deuterium. This can account for the isotope enhancement factors. In addition, preliminary results from sawtooth propagation in both hard and soft X-ray monitors supports the former proposition. To outline this, firstly the isotope documentation in the TJ-I tokamak is reported and then a plausible interpretation within a magnetic transport model is discussed. (author) 6 refs., 4 figs

  4. Insights into early Earth from Barberton komatiites: Evidence from lithophile isotope and trace element systematics

    Science.gov (United States)

    Puchtel, I. S.; Blichert-Toft, J.; Touboul, M.; Walker, R. J.; Byerly, G. R.; Nisbet, E. G.; Anhaeusser, C. R.

    2013-05-01

    Major, minor, and lithophile trace element abundances and Nd and Hf isotope systematics are reported for two sets of remarkably fresh, by Archean standards, samples of komatiitic lavas from the 3.48 Ga Komati and the 3.27 Ga Weltevreden Formations of the Barberton Greenstone Belt (BGB) in South Africa. These data are used to place new constraints on the thermal history of the early Archean mantle, on the timing of its differentiation, and on the origin and chemical nature of early mantle reservoirs and their evolution through time. Projected moderate to strong depletions of highly incompatible lithophile trace elements and water in the mantle sources of both komatiite systems, combined with the partitioning behavior of V during lava differentiation, are consistent with anhydrous conditions during generation of the komatiite magmas. Komati and Weltevreden lavas are inferred to have erupted with temperatures of ∼1600 °C, and, thus, represent the hottest known lavas on Earth. The calculated mantle potential temperatures of ∼1800 °C for both komatiite systems are 150-200 °C higher than those of contemporary ambient mantle. Combined, these observations are consistent with the origin of these BGB komatiite magmas in mantle plumes in the lower mantle. New Sm-Nd and Lu-Hf isotopic data allow precise determination of initial ε143Nd = +0.46 ± 0.10 and +0.50 ± 0.11 and initial ε176Hf = +1.9 ± 0.3 and +4.7 ± 0.8 for the Komati and the Weltevreden system komatiites, respectively. These positive initial values reflect prior fractionation of Sm/Nd and Lu/Hf in the mantle early in Earth history. Conversely, μ142Nd values are 0.0 ± 2.4 and +2.2 ± 4.1 for the Komati and the Weltevreden systems, respectively. These values overlap, within uncertainties, those of modern terrestrial rocks, thus, limiting the magnitudes of possible Sm/Nd fractionations generated by early Earth processes in the sources of these rocks. Combined 142,143Nd and Hf isotope and lithophile trace

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

    Science.gov (United States)

    Usui, Tomohiro; Alexander, Conel M. O'D.; Wang, Jianhua; Simon, Justin I.; Jones, John H.

    2015-01-01

    The surface geology and geomorphology of Mars indicates that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have conducted in situ hydrogen isotope (D/H) analyses of quenched and impact glasses in three Martian meteorites (Yamato 980459, EETA79001, LAR 06319) by Cameca ims-6f at Digital Terrain Models (DTM) following the methods of [1]. The hydrogen isotope analyses provide evidence for the existence of a distinct but ubiquitous water/ice reservoir (D/H = 2-3 times Earth's ocean water: Standard Mean Ocean Water (SMOW)) that lasted from at least the time when the meteorites crystallized (173-472 Ma) to the time they were ejected by impacts (0.7-3.3 Ma), but possibly much longer [2]. The origin of this reservoir appears to predate the current Martian atmospheric water (D/H equals approximately 5-6 times SMOW) and is unlikely to be a simple mixture of atmospheric and primordial water retained in the Martian mantle (D/H is approximately equal to SMOW [1]). Given the fact that this intermediate-D/H reservoir (2-3 times SMOW) is observed in a diverse range of Martian materials with different ages (e.g., SNC (Shergottites, Nakhlites, Chassignites) meteorites, including shergottites such as ALH 84001; and Curiosity surface data [3]), we conclude that this intermediate-D/H reservoir is likely a global surficial feature that has remained relatively intact over geologic time. We propose that this reservoir represents either hydrated crust and/or ground ice interbedded within sediments. Our results corroborate the hypothesis that a buried cryosphere accounts for a large part of the initial water budget of Mars.

  6. Occurrence of fossil organic matter in modern environments: Optical, geochemical and isotopic evidence

    Energy Technology Data Exchange (ETDEWEB)

    Graz, Y., E-mail: Christian.Di-Giovanni@univ-orleans.fr [ISTO, Universite d' Orleans/Universite Francois Rabelais de Tours, CNRS/INSU UMR 6113, 1A rue de la Ferollerie, 45072 Orleans (France); Di-Giovanni, C. [ISTO, Universite d' Orleans/Universite Francois Rabelais de Tours, CNRS/INSU UMR 6113, 1A rue de la Ferollerie, 45072 Orleans (France); Copard, Y. [M2C, UMR 6143 CNRS/Universite de Rouen, place E. Blondel, Bat. Irese A, Universite de Rouen, 76821 Mont Saint Aignan Cedex (France); Elie, M.; Faure, P. [G2R UMR 7566 CNRS/Universite Henri Poincare, BP 239, 54506 Vandoeuvre-les-Nancy Cedex (France); Laggoun Defarge, F. [ISTO, Universite d' Orleans/Universite Francois Rabelais de Tours, CNRS/INSU UMR 6113, 1A rue de la Ferollerie, 45072 Orleans (France); Leveque, J. [UMR A111 INRA/Universite de Bourgogne - GeoSol, 6 bd Gabriel, 21000 Dijon (France); Michels, R. [G2R UMR 7566 CNRS/Universite Henri Poincare, BP 239, 54506 Vandoeuvre-les-Nancy Cedex (France); Olivier, J.E. [CEMAGREF, Grenoble, Unite de recherche ETNA, BP 76, 38402 Saint Martin d' Heres (France)

    2011-08-15

    Highlights: > Fossil organic matter contribution is significant in some modern carbon pools (soils or riverine particles). > Fossil organic matter fate appears to be controlled by the nature of the weathering processes. > The physical and chemical properties of fossil organic matter lead to a variation of its sensitivity toward weathering. - Abstract: This study relates to the input and fate of fossil organic matter (FOM) in the modern environment, and focuses on two experimental watersheds overlying Jurassic marls: Le Laval and Le Brusquet (1 km{sup 2} in area), located near Digne, Alpes-de-Haute-Provence, France. Considering that FOM delivery is mainly a result of different processes affecting sedimentary rocks [(bio)chemical and mechanical weathering], samples from different pools were collected: bedrocks, weathering profiles, soils and riverine particles. The samples were examined using complementary techniques: optical (palynofacies methods), geochemical (Rock-Eval 6 pyrolysis, C/N ratio), molecular (gas chromatography/mass spectrometry) and isotopic (stable C isotopic composition). As a result, FOM markers were identified and tracked through the different pools. The results highlight the contribution of FOM, which can be found in all the studied pools. Transfer of FOM between bedrocks/weathering profiles (governed mainly by chemical weathering) and bedrocks/riverine particles (governed mainly by mechanical weathering) reveals any qualitative change. Weathering profiles/soils transition [governed by (bio)chemical weathering] is characterized by alteration of the FOM, which is difficult to describe because fossil material is mixed with recent organic matter (ROM). Despite this latter point, the study provides evidence for a relative resistance of FOM to weathering processes and points to its contribution to the modern geosystem and the C cycle.

  7. Upper Paleozoic oceanic crust in the Polish Sudetes: NdSr isotope and trace element evidence

    Science.gov (United States)

    Pin, C.; Majerowicz, A.; Wojciechowska, I.

    1988-03-01

    The two main mafic-ultramafic complexes outcropping in the Polish Sudetes around the Sowie Góry high-grade massif (Mt. Sleza and Nowa Ruda) have been studied for trace elements and NdSr isotopes. Upper Paleozoic SmNd whole-rock isochron ages are obtained for both massifs: 353 ± 21 Ma (2σ) with ɛi = + 8.8 ± 0.1 (Mt. Sleza) and 351 ± 16 Ma with ɛi = 8.5 ± 0.1 (Nowa Ruda). The high initial ɛNd point to a source characterized by a strong time-integrated LREE depletion and, along with incompatible trace-element patterns, they substantiate the oceanic derivation of these massifs. Although a subduction-related marginal basin setting cannot be totally precluded, trace-element and isotopic data rather suggest a normal mid-ocean ridge origin for the Sudetic ophiolites. While these results are in marked contrast with previously inferred Precambrian or early Paleozoic ages, remnants of oceanic crust as young as the Early Carboniferous are consistent with the local sedimentary record of pelagic facies from the Frasnian to the Tournaisian, and they may provide a suitable explanation for the contrasted evolution displayed by different domains of the Sudetes. The Sudetic ophiolites might tentatively be correlated with the upper Paleozoic "prasinites" of the Saxon Lineament if a Late Hercynian ca. 150 km dextral offset is assumed along the Elbe Fracture. In that case, they might represent the latest-stage remnants of an oceanic suture zone between the Saxo-Thuringian and Moldanubian zones. Together with several other examples throughout Europe, these ophiolites provide compelling evidence for the involvement of oceanic crust and plate-tectonic processes in the Variscan belt.

  8. Electronic isotope effects in the palladium-hydrogen system

    International Nuclear Information System (INIS)

    Oppeneer, P.M.

    1987-01-01

    The main objective of this investigation is the determination of the physical origin of the isotope effects measured in the de Haas-van Alphen quantities of dilute Pd(H), Pd(D) and Pd(T) alloys. A computational method for the numerical evaluation of interstitial Green functions, which are indispensable for the descriptions of interactions of conducting electrons with interstitial atoms, is presented. The Green functions are tested in ab initio calculations of the dHvA quantities for the frozen interstitial impurities H, B and C in Pd using a KKR-Green function formulation for interstitial effects. The results are in good agreement with the experimental data and it is concluded that the interstitial Green functions, in combination with the KKR-Green function approach, are applicable for the description of electron scattering by interstitial defects. The influence of zero-point motion of a light interstitial on the electron scattering is evaluated in a computational model. Computations show that the influence on the dHvA quantities is quite small. The anharmonicity of the octahedral potential well in a Pd lattice is considered because it can cause differences in the vibrational properties of hydrogen isotopes. The influence of resonant vibrations on the electron-defect scattering is investigated. It is shown that the occurrence of a resonant mode depends sensitively on the isotope's mass and force constants. It is concluded that the isotope effect in dHvA quantities can be explained by the occurrence of a low-frequency resonant vibration in the Pd(D) system. 264 refs.; 9 figs.; 10 tabs

  9. Carbon-13 isotope effects on 199Hg nuclear shielding

    International Nuclear Information System (INIS)

    Sebald, Angelika; Wrackmeyer, Bernd

    1985-01-01

    Secondary 13 C/ 12 C isotope effects on 199 Hg nuclear shielding (Δdeltasup(i)( 199 Hg)) are of interest because of the unusual shift to high frequency which has been observed for a few alkyl mercury compounds. Continuing interest in the NMR parameters of mercury compounds prompted a search for the values Δdeltasup(i)( 199 Hg) in a greater variety of organomercurials. This should help to find out about the range of Δdeltasup(i)( 199 Hg) and to obtain a firmer basis for the discussion of the high-frequency shifts. The data and experimental conditions are given for chemical shifts delta 199 Hg, coupling constants sup(n)J( 199 Hg 13 C) and 13 C/ 12 C isotope shifts Δdeltasup(i)( 199 Hg) of fourteen 199 Hg organomercury compounds. The results are discussed. (author)

  10. Selected bibliography on deuterium isotope effects and heavy water

    International Nuclear Information System (INIS)

    Dave, S.M.; Donde, M.M.

    1983-01-01

    In recent years, there has been a great deal of interest in using deuterium and heavy water not only in nuclear industry but also in various fields of basic as well as applied research in physics, chemistry and biology. As a result, the literature is being enriched with a large number of research papers and technical reports published each year. Thus, to enable the scientists to have an easy reference to these works, an endeavour has been made in this selected bibliography, to enlist the publications related to these fields. Since the interest is concerned mainly with heavy water production processes, deuterium isotope effects etc., several aspects (e.g. nuclear) of deuterium have not been covered here. The material in this bibliography which cites 2388 references has been classified under six broad headings, viz. (1) Production of heavy water, (2) Study of deuterium isotope effects, (3) Analysis and Properties of heavy water, (4) Laser Separation of deuterium, (5) Isotopic exchange reactions, and (6) Miscellaneous. The sources of information used for this compilation are chemical abstracts, nuclear science abstracts, INIS Atomindex and also some scattered search through journals and reports available in the B.A.R.C. library. However, in spite of sincere attempts for a wide coverage, no claim is being made towards the exhaustiveness of this bibliography. (author)

  11. Kinetic isotope effects and how to describe them

    Directory of Open Access Journals (Sweden)

    Konstantin Karandashev

    2017-11-01

    Full Text Available We review several methods for computing kinetic isotope effects in chemical reactions including semiclassical and quantum instanton theory. These methods describe both the quantization of vibrational modes as well as tunneling and are applied to the ⋅H + H2 and ⋅H + CH4 reactions. The absolute rate constants computed with the semiclassical instanton method both using on-the-fly electronic structure calculations and fitted potential-energy surfaces are also compared directly with exact quantum dynamics results. The error inherent in the instanton approximation is found to be relatively small and similar in magnitude to that introduced by using fitted surfaces. The kinetic isotope effect computed by the quantum instanton is even more accurate, and although it is computationally more expensive, the efficiency can be improved by path-integral acceleration techniques. We also test a simple approach for designing potential-energy surfaces for the example of proton transfer in malonaldehyde. The tunneling splittings are computed, and although they are found to deviate from experimental results, the ratio of the splitting to that of an isotopically substituted form is in much better agreement. We discuss the strengths and limitations of the potential-energy surface and based on our findings suggest ways in which it can be improved.

  12. Neutron skin effect of some Mo isotopes in pre-equilibrium reactions

    Indian Academy of Sciences (India)

    The neutron skin effect has been investigated for even isotopes of molybdenum at 25.6. MeV 94−100Mo(p,xn) ... exciton numbers from different radii of even Mo isotopes were used to obtain the corresponding neutron ..... nical applications such as the isotope production alternatives (for producing medical ra- dioisotopes ...

  13. Detuning effect in multistep photo-ionization of atomic isotope of heavy element

    International Nuclear Information System (INIS)

    Wakaida, Ikuo; Akaoka, Katsuaki; Miyabe, Masabumi; Oba, Masaki; Arisawa, Takashi

    1995-01-01

    Detuning effect on the excitation wavelength in 3-step photoionization of atomic isotope of heavy element was experimentally obtained and the role of the isotope shift and hyperfine structure in each transition level was discussed. To achieve high selectivity, the combination of the HFS and isotope sift of upper and lower energy level including the autoionizing level was important. (author)

  14. OXYGEN ISOTOPIC COMPOSITIONS OF THE ALLENDE TYPE C CAIs: EVIDENCE FOR ISOTOPIC EXCHANGE DURING NEBULAR MELTING AND ASTEROIDAL THERMAL METAMORPHISM

    Energy Technology Data Exchange (ETDEWEB)

    Krot, A N; Chaussidon, M; Yurimoto, H; Sakamoto, N; Nagashima, K; Hutcheon, I D; MacPherson, G J

    2008-02-21

    Based on the mineralogy and petrography, coarse-grained, igneous, anorthite-rich (Type C) calcium-aluminum-rich inclusions (CAIs) in the CV3 carbonaceous chondrite Allende have been recently divided into three groups: (i) CAIs with melilite and Al,Ti-diopside of massive and lacy textures (coarse grains with numerous rounded inclusions of anorthite) in a fine-grained anorthite groundmass (6-1-72, 100, 160), (ii) CAI CG5 with massive melilite, Al,Ti-diopside and anorthite, and (iii) CAIs associated with chondrule material: either containing chondrule fragments in their peripheries (ABC, TS26) or surrounded by chondrule-like, igneous rims (93) (Krot et al., 2007a,b). Here, we report in situ oxygen isotopic measurements of primary (melilite, spinel, Al,Ti-diopside, anorthite) and secondary (grossular, monticellite, forsterite) minerals in these CAIs. Spinel ({Delta}{sup 17}O = -25{per_thousand} to -20{per_thousand}), massive and lacy Al,Ti-diopside ({Delta}{sup 17}O = -20{per_thousand} to -5{per_thousand}) and fine-grained anorthite ({Delta}{sup 17}O = -15{per_thousand} to -2{per_thousand}) in 100, 160 and 6-1-72 are {sup 16}O-enriched relative spinel and coarse-grained Al,Ti-diopside and anorthite in ABC, 93 and TS26 ({Delta}{sup 17}O ranges from -20{per_thousand} to -15{per_thousand}, from -15{per_thousand} to -5{per_thousand}, and from -5{per_thousand} to 0{per_thousand}, respectively). In 6-1-72, massive and lacy Al,Ti-diopside grains are {sup 16}O-depleted ({Delta}{sup 17}O {approx} -13{per_thousand}) relative to spinel ({Delta}{sup 17}O = -23{per_thousand}). Melilite is the most {sup 16}O-depleted mineral in all Allende Type C CAIs. In CAI 100, melilite and secondary grossular, monticellite and forsterite (minerals replacing melilite) are similarly {sup 16}O-depleted, whereas grossular in CAI 160 is {sup 16}O-enriched ({Delta}{sup 17}O = -10{per_thousand} to -6{per_thousand}) relative to melilite ({Delta}{sup 17}O = -5{per_thousand} to -3{per_thousand}). We infer

  15. Magnetic field and magnetic isotope effects on photochemical reactions

    International Nuclear Information System (INIS)

    Wakasa, Masanobu

    1999-01-01

    By at present exact experiments and the theoretical analysis, it was clear that the magnetic field less than 2 T affected a radical pair reaction and biradical reaction. The radical pair life and the dissipative radical yield showed the magnetic field effects on chemical reactions. The radical pair mechanism and the triplet mechanism were known as the mechanism of magnetic field effects. The radical pair mechanism consists of four mechanisms such as the homogeneous hyperfine interaction (HFC), the delta-g mechanism, the relaxation mechanism and the level cross mechanism. In order to observe the magnetic effects of the radical pair mechanism, two conditions need, namely, the recombination rate of singlet radical pair > the dissipation rate and the spin exchange rate > the dissipation rate. A nanosecond laser photo-decomposition equipment can observe the magnetic field effects. The inversion phenomena of magnetic field effect, isolation of the relaxation mechanism and the delta-g mechanism, the magnetic field effect of heavy metal radical reaction, the magnetic field effect in homogeneous solvent, saturation of delta-g mechanism are explained. The succeeded examples of isotope concentration by the magnetic isotope effect are 17 O, 19 Si, 33 S, 73 Ge and 235 U. (S.Y.)

  16. Gallium isotopic evidence for extensive volatile loss from the Moon during its formation

    OpenAIRE

    Kato, Chizu; Moynier, Fr?d?ric

    2017-01-01

    The distribution and isotopic composition of volatile elements in planetary materials holds a key to the characterization of the early solar system and the Moon's formation. The Moon and Earth are chemically and isotopically very similar. However, the Moon is highly depleted in volatile elements and the origin of this depletion is still debated. We present gallium isotopic and elemental measurements in a large set of lunar samples to constrain the origin of this volatile depletion. We show th...

  17. Post-eruptive alteration of silicic ignimbrites and lavas, Gran Canaria, Canary Islands - Strontium, neodymium, lead, and oxygen isotopic evidence

    Science.gov (United States)

    Cousens, Brian L.; Spera, Frank J.; Dobson, Patrick F.

    1993-01-01

    The isotopic composition of lavas from oceanic islands provides important information about the composition and evolution of the earth's mantle. Isotopic analyses of Miocene comenditic, pantelleritic, and trachyphonolitic ignimbrites and lavas from the Canary islands were performed. Results provide evidence for posteruptive mobility of Rb and Sr during low temperature postemplacement interaction with circulating ground water. Calculated Sr isotope ratios define a magmatic trend in the stratigraph section. 87Sr/86Sr ratios in hydrated vitrophyte and devitrified matrix separates indicate significant posteruptive interaction with meteoric water starting soon after deposition. This process extends patchily through the entire pyroclastic flow and may be ongoing. 87Sr/86Sr ratios determined by whole rock analysis of silicic rocks from oceanic islands are suspect and should not be incorporated into mantle tracer studies. Anorthoclase phenocrysts are resistant to these processes and may produce useful data.

  18. Evidence from stable isotopes and10Be for solar system formation triggered by a low-mass supernova.

    Science.gov (United States)

    Banerjee, Projjwal; Qian, Yong-Zhong; Heger, Alexander; Haxton, W C

    2016-11-22

    About 4.6 billion years ago, some event disturbed a cloud of gas and dust, triggering the gravitational collapse that led to the formation of the solar system. A core-collapse supernova, whose shock wave is capable of compressing such a cloud, is an obvious candidate for the initiating event. This hypothesis can be tested because supernovae also produce telltale patterns of short-lived radionuclides, which would be preserved today as isotopic anomalies. Previous studies of the forensic evidence have been inconclusive, finding a pattern of isotopes differing from that produced in conventional supernova models. Here we argue that these difficulties either do not arise or are mitigated if the initiating supernova was a special type, low in mass and explosion energy. Key to our conclusion is the demonstration that short-lived 10 Be can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed.

  19. Evidence from stable isotopes and 10Be for solar system formation triggered by a low-mass supernova

    Science.gov (United States)

    Banerjee, Projjwal; Qian, Yong-Zhong; Heger, Alexander; Haxton, W. C.

    2016-11-01

    About 4.6 billion years ago, some event disturbed a cloud of gas and dust, triggering the gravitational collapse that led to the formation of the solar system. A core-collapse supernova, whose shock wave is capable of compressing such a cloud, is an obvious candidate for the initiating event. This hypothesis can be tested because supernovae also produce telltale patterns of short-lived radionuclides, which would be preserved today as isotopic anomalies. Previous studies of the forensic evidence have been inconclusive, finding a pattern of isotopes differing from that produced in conventional supernova models. Here we argue that these difficulties either do not arise or are mitigated if the initiating supernova was a special type, low in mass and explosion energy. Key to our conclusion is the demonstration that short-lived 10Be can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed.

  20. Isotope enrichment effect of gaseous mixtures in standing sound vibration

    International Nuclear Information System (INIS)

    Knesebeck, R.L.

    1984-01-01

    When standing acoustic waves are excited in a tube containing a mixture of two gases, a partial zonal fractioning of the components arises as consequence of mass transport by diffusion, driven by the thermal and pressure gradients which are associeted with the standing waves. This effect is present in each zone corresponding to a quarter wavelength, with the heavier component becoming enriched at the nodes fo the standing waves and deplected at the crests. The magnitude of the enrichment in one of the components of a binary gas mixture is given by Δω=ap 2 /lambda [b + (1-bω)] 2 . Where ω is the mass concentration of the component in the mixture, a and b are parameters which are related to molecular proprieties of the gases, p is the relative pressure amplitude of the standing wave and lambda is its wavelength. For a natural mixture of uranium hexafluorate, with 0.715% of the uranium isotope 340 an enrichment of about 2 x 10 -6 % in the concentration of this isotope is theorecticaly attainable per stage consisting of a quarter wavelenght, when a standing acoustical wave of relative pressure amplitude of 0,2 and wavelenght of 20 cm is used. Since standing acoustical waves are easely excited in gas columns, an isotope enrichment plant made of a cascade of tubes in which standing waves are excited, is presumably feasible with relatively low investment and operation costs. (Author) [pt

  1. On the Effect of Planetary Stable Isotope Compositions on Growth and Survival of Terrestrial Organisms.

    Directory of Open Access Journals (Sweden)

    Xueshu Xie

    Full Text Available Isotopic compositions of reactants affect the rates of chemical and biochemical reactions. Usually it is assumed that heavy stable isotope enrichment leads to progressively slower reactions. Yet the effect of stable isotopes may be nonlinear, as exemplified by the "isotopic resonance" phenomenon. Since the isotopic compositions of other planets of Solar system, including Mars and Venus, are markedly different from terrestrial (e.g., deuterium content is ≈5 and ≈100 times higher, respectively, it is far from certain that terrestrial life will thrive in these isotopic conditions. Here we found that Martian deuterium content negatively affected survival of shrimp in semi-closed biosphere on a year-long time scale. Moreover, the bacterium Escherichia coli grows slower at Martian isotopic compositions and even slower at Venus's compositions. Thus, the biological impact of varying stable isotope compositions needs to be taken into account when planning interplanetary missions.

  2. Deduction of kinetic mechanism in multisubstrate enzyme reactions from tritium isotope effects. Application to dopamine beta-hydroxylase

    International Nuclear Information System (INIS)

    Klinman, J.P.; Humphries, H.; Voet, J.G.

    1980-01-01

    Primary tritium isotope effects have been measured for the hydroxylation of [2-3H] dopamine catalyzed by dopamine beta-hydroxylase. Experimental values vary from 8.8 +/- 1.4 at 0.02 mM oxygen to 4.1 +/- 0.6 at 1.0 mM oxygen. It is shown that the observed dependence of the isotope effect on oxygen concentration provides unequivocal evidence for a kinetically significant dissociation of both dopamine and oxygen from enzyme, ternary complex. This approach, which is applicable to any multisubstrate enzyme characterized by detectable kinetic isotope effects, provides an alternate to classical methods for the elucidation of kinetic order in enzyme-catalyzed reactions

  3. Effect of ecological conditions on migration of thorium isotopes isotopes in the soil-plant system

    International Nuclear Information System (INIS)

    Shuktomova, I.I.; Titaeva, N.A.; Kochan, I.G.

    1994-01-01

    Two territories (zones of central taiga and mountainous tundra) with a high natural content of thorium in soil forming rock and soil were examined in comparative analysis of fixed state and behavior of thorium isotopes ( 232 Th, 230 Th, 228 Th, 227 Th) in the soil layer and rock including evaluation and nature of distribution and forms of presence of isotopes in soil profiles; the extent of participance of isotopes in soil-forming processes is discussed and several conclusions are made regarding the role of genesis of isotopes and parameters of the migration medium for the direction and rate of migration processes. It was found that both climatic zones are characterized by the inclusion of all thorium isotopes in the biological cycle in the soil--plant systems. Characterizing as a whole the build up up thorium isotopes in all examined vegetation of the tundra, it may be noted that it is characterized by a slightly different dependence of mobility of these isotopes in comparison with the vegetation of the taiga zone. In addition, the intensity of inclusion of these thorium isotopes in the biological cycles of migration in the taiga zones is higher than in the tundra zone. 3 refs., 4 tabs

  4. Mobility and diet in Neolithic, Bronze Age and Iron Age Germany : evidence from multiple isotope analysis

    NARCIS (Netherlands)

    Oelze, Viktoria Martha

    2012-01-01

    Prehistoric human diet can be reconstructed by the analysis of carbon (C), nitrogen (N) and sulphur (S) stable isotopes in bone, whereas ancient mobility and provenance can be studied using the isotopes of strontium (Sr) and oxygen (O) in tooth enamel, and of sulphur in bone. Although thirty years

  5. Isotope effects in ice Ih: A path-integral simulation

    Science.gov (United States)

    Herrero, Carlos P.; Ramírez, Rafael

    2011-03-01

    Ice Ih has been studied by path-integral molecular dynamics simulations, using the effective q-TIP4P/F potential model for flexible water. This has allowed us to analyze finite-temperature quantum effects in this solid phase from 25 to 300 K at ambient pressure. Among these effects we find a negative thermal expansion of ice at low temperatures, which does not appear in classical molecular dynamics simulations. The compressibility derived from volume fluctuations gives results in line with experimental data. We have analyzed isotope effects in ice Ih by considering normal, heavy, and tritiated water. In particular, we studied the effect of changing the isotopic mass of hydrogen on the kinetic energy and atomic delocalization in the crystal as well as on structural properties such as interatomic distances and molar volume. For D2O ice Ih at 100 K we obtained a decrease in molar volume and intramolecular O-H distance of 0.6% and 0.4%, respectively, as compared to H2O ice.

  6. Isotope effects in ice Ih: a path-integral simulation.

    Science.gov (United States)

    Herrero, Carlos P; Ramírez, Rafael

    2011-03-07

    Ice Ih has been studied by path-integral molecular dynamics simulations, using the effective q-TIP4P/F potential model for flexible water. This has allowed us to analyze finite-temperature quantum effects in this solid phase from 25 to 300 K at ambient pressure. Among these effects we find a negative thermal expansion of ice at low temperatures, which does not appear in classical molecular dynamics simulations. The compressibility derived from volume fluctuations gives results in line with experimental data. We have analyzed isotope effects in ice Ih by considering normal, heavy, and tritiated water. In particular, we studied the effect of changing the isotopic mass of hydrogen on the kinetic energy and atomic delocalization in the crystal as well as on structural properties such as interatomic distances and molar volume. For D(2)O ice Ih at 100 K we obtained a decrease in molar volume and intramolecular O-H distance of 0.6% and 0.4%, respectively, as compared to H(2)O ice. © 2011 American Institute of Physics.

  7. Malic enzyme: Tritium isotope effects with alternative dinucleotide substrates and divalent metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Karsten, W.E.; Harris, B.G.; Cook, P.F. (Texas College of Osteopathic Medicine, Fort Worth (United States))

    1992-01-01

    The NAD-malic enzyme from Ascaris suum catalyzes the divalent metal ion dependent oxidative decarboxylation of L-malate to yield pyruvate, carbon dioxide and NADH. Multiple isotope effect studies suggest a stepwise chemical mechanism with hydride transfer from L-malate to NAD occurring first to form oxalacetate, followed by decarboxylation. Utilizing L-malate-2-T, tritium V/K isotope effects have been determined for the hydride transfer step using a variety of alternative dinucleotide substrates and divalent metal ions. Combination of these data with deuterium isotope effects data and previously determined [sup 13]C isotope effects has allowed the calculation of intrinsic isotope effects for the malic enzyme catalyzed reaction. The identity of both the dinucleotide substrate and divalent metal ion has an effect of the size of the intrinsic isotope effect for hydride transfer.

  8. Malic enzyme: Tritium isotope effects with alternative dinucleotide substrates and divalent metal ions

    International Nuclear Information System (INIS)

    Karsten, W.E.; Harris, B.G.; Cook, P.F.

    1992-01-01

    The NAD-malic enzyme from Ascaris suum catalyzes the divalent metal ion dependent oxidative decarboxylation of L-malate to yield pyruvate, carbon dioxide and NADH. Multiple isotope effect studies suggest a stepwise chemical mechanism with hydride transfer from L-malate to NAD occurring first to form oxalacetate, followed by decarboxylation. Utilizing L-malate-2-T, tritium V/K isotope effects have been determined for the hydride transfer step using a variety of alternative dinucleotide substrates and divalent metal ions. Combination of these data with deuterium isotope effects data and previously determined 13 C isotope effects has allowed the calculation of intrinsic isotope effects for the malic enzyme catalyzed reaction. The identity of both the dinucleotide substrate and divalent metal ion has an effect of the size of the intrinsic isotope effect for hydride transfer

  9. Degassing, crystallization and eruption dynamics at Stromboli: trace element and lithium isotopic evidence from 2003 ashes

    Science.gov (United States)

    Schiavi, Federica; Kobayashi, Katsura; Moriguti, Takuya; Nakamura, Eizo; Pompilio, Massimo; Tiepolo, Massimo; Vannucci, Riccardo

    2010-04-01

    During its 1800-year-long persistent activity the Stromboli volcano has erupted a highly porphyritic (HP) volatile-poor scoriaceous magma and a low porphyritic (LP) volatile-rich pumiceous magma. The HP magma is erupted during normal Strombolian explosions and lava effusions, while the LP one is related to more energetic paroxysms. During the March-April 2003 explosive activity, Stromboli ejected two typologies of juvenile glassy ashes, namely highly vesicular LP shards and volatile-poor HP shards. Their textural and in situ chemical characteristics are used to unravel mutual relationships between HP and LP magmas, as well as magma dynamics within the shallow plumbing system. The mantle-normalized trace element patterns of both ash types show the typical arc-lava pattern; however, HP glasses possess incompatible element concentrations higher than LP glasses, along with Sr and Eu negative anomalies. HP shards are generally characterized by higher Li contents (to ~20 ppm) and lower δ7Li values (+1.2 to -3.8‰) with respect to LP shards (Li contents of 7-14 ppm and δ7Li ranging between +4.6 and +0.9‰). Fractional crystallization models based on major and trace element compositions, combined with a degassing model based on open-system Rayleigh distillation and on the assumption that melt/fluidDLi > 1, show that abundant (~30%) plagioclase precipitation and variable degrees of degassing can lead the more primitive LP magma to evolve toward a differentiated (isotopically lighter) HP magma ponding in the upper conduit and undergoing slow continuous degassing-induced crystallization. This study also evidences that in March 2003 Stromboli volcano poured out a small early volume of LP magma that traveled slower within the conduit with respect to later and larger volumes of fast ascending LP magma erupted during the April 5 paroxysm. The different ascent rates and cooling rates of the two LP magma batches (i.e., pre- and post-paroxysm) resulted in small, but detectable

  10. Sources and transformations of nitrate from streams draining varying land uses: evidence from dual isotope analysis.

    Science.gov (United States)

    Burns, Douglas A; Boyer, Elizabeth W; Elliott, Emily M; Kendall, Carol

    2009-01-01

    Knowledge of key sources and biogeochemical processes that affect the transport of nitrate (NO(3)(-)) in streams can inform watershed management strategies for controlling downstream eutrophication. We applied dual isotope analysis of NO(3)(-) to determine the dominant sources and processes that affect NO(3)(-) concentrations in six stream/river watersheds of different land uses. Samples were collected monthly at a range of flow conditions for 15 mo during 2004-05 and analyzed for NO(3)(-) concentrations, delta(15)N(NO3), and delta(18)O(NO3). Samples from two forested watersheds indicated that NO(3)(-) derived from nitrification was dominant at baseflow. A watershed dominated by suburban land use had three delta(18)O(NO3) values greater than +25 per thousand, indicating a large direct contribution of atmospheric NO(3)(-) transported to the stream during some high flows. Two watersheds with large proportions of agricultural land use had many delta(15)N(NO3) values greater than +9 per thousand, suggesting an animal waste source consistent with regional dairy farming practices. These data showed a linear seasonal pattern with a delta(18)O(NO3):delta (15)N(NO3) of 1:2, consistent with seasonally varying denitrification that peaked in late summer to early fall with the warmest temperatures and lowest annual streamflow. The large range of delta (15)N(NO3) values (10 per thousand) indicates that NO(3)(-) supply was likely not limiting the rate of denitrification, consistent with ground water and/or in-stream denitrification. Mixing of two or more distinct sources may have affected the seasonal isotope patterns observed in these two agricultural streams. In a mixed land use watershed of large drainage area, none of the source and process patterns observed in the small streams were evident. These results emphasize that observations at watersheds of a few to a few hundred km(2) may be necessary to adequately quantify the relative roles of various NO(3)(-) transport and

  11. Potassium isotopic evidence for a high-energy giant impact origin of the Moon.

    Science.gov (United States)

    Wang, Kun; Jacobsen, Stein B

    2016-10-27

    The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

  12. Atmospheric evidence for a global secular increase in carbon isotopic discrimination of land photosynthesis

    Science.gov (United States)

    Keeling, Ralph F.; Graven, Heather D.; Welp, Lisa R.; Resplandy, Laure; Bi, Jian; Piper, Stephen C.; Sun, Ying; Bollenbacher, Alane; Meijer, Harro A. J.

    2017-09-01

    A decrease in the 13C/12C ratio of atmospheric CO2 has been documented by direct observations since 1978 and from ice core measurements since the industrial revolution. This decrease, known as the 13C-Suess effect, is driven primarily by the input of fossil fuel-derived CO2 but is also sensitive to land and ocean carbon cycling and uptake. Using updated records, we show that no plausible combination of sources and sinks of CO2 from fossil fuel, land, and oceans can explain the observed 13C-Suess effect unless an increase has occurred in the 13C/12C isotopic discrimination of land photosynthesis. A trend toward greater discrimination under higher CO2 levels is broadly consistent with tree ring studies over the past century, with field and chamber experiments, and with geological records of C3 plants at times of altered atmospheric CO2, but increasing discrimination has not previously been included in studies of long-term atmospheric 13C/12C measurements. We further show that the inferred discrimination increase of 0.014 ± 0.007‰ ppm-1 is largely explained by photorespiratory and mesophyll effects. This result implies that, at the global scale, land plants have regulated their stomatal conductance so as to allow the CO2 partial pressure within stomatal cavities and their intrinsic water use efficiency to increase in nearly constant proportion to the rise in atmospheric CO2 concentration.

  13. Gallium isotopic evidence for extensive volatile loss from the Moon during its formation.

    Science.gov (United States)

    Kato, Chizu; Moynier, Frédéric

    2017-07-01

    The distribution and isotopic composition of volatile elements in planetary materials holds a key to the characterization of the early solar system and the Moon's formation. The Moon and Earth are chemically and isotopically very similar. However, the Moon is highly depleted in volatile elements and the origin of this depletion is still debated. We present gallium isotopic and elemental measurements in a large set of lunar samples to constrain the origin of this volatile depletion. We show that while Ga has a geochemical behavior different from zinc, both elements show a systematic enrichment in the heavier isotopes in lunar mare basalts and Mg-suite rocks compared to the silicate Earth, pointing to a global-scale depletion event. On the other hand, the ferroan anorthosites are isotopically heterogeneous, suggesting a secondary distribution of Ga at the surface of the Moon by volatilization and condensation. The isotopic difference of Ga between Earth and the Moon and the isotopic heterogeneity of the crustal ferroan anorthosites suggest that the volatile depletion occurred following the giant impact and during the lunar magma ocean phase. These results point toward a Moon that has lost its volatile elements during a whole-scale evaporation event and that is now relatively dry compared to Earth.

  14. Relative extents of hydrogen-deuterium exchange of nitrosamines: relevance to biological isotope effect studies

    International Nuclear Information System (INIS)

    Singer, G.M.; Lijinsky, W.

    1979-01-01

    Relative extents of base-catalyzed, hydrogen-deuterium exchange have been determined for a number of nitrosamines. Observed trends in the exchanges are discussed in terms of substitution, ring size and conformation. The relevance of the exchanges to deuterium isotope effects in carcinogenesis tests is discussed. Those compounds which give pronounced biological isotope effects undergo exchange only to a small extent. No biological isotope effect is found for compounds which undergo extensive exchange. (author)

  15. Nagssugtoqidian mobile belt of West Greenland: A cryptic 1850 Ma suture between two Archaean continents - chemical and isotopic evidence

    International Nuclear Information System (INIS)

    Kalsbeek, F.; Pidgeon, R.T.; Taylor, P.N.

    1987-01-01

    New chemical and isotopic data permit the recognition of a cryptic suture zone between two Archean continental masses within the Nagssugtoqidian mobile belt of West Greenland. This discovery has important implications for Precambrian crustal evolution: suture zones may not always be identifiable from geologic field observations, with the consequence that mobile belts in which undetected sutures exist may be mis-identified as ensialic, and thought to require special non-plate tectonic models to account for their development. The Nagssugtoqidian belt consists mainly of Archaean gneisses reworked during the Proterozoic, with metamorphic grade and degree of isotopic disturbance increasing towards the center of the belt. At the centre of the belt the Nagssugtoqidian includes metasediments and calc-alkaline volcanic and plutonic rocks of Proterozoic age, almost always strongly deformed and metamorphosed. From isotopic evidence (Sr i ca. 0.703; model μ 1 values ca. 8.0; initial ε Nd ca. 0) it is clear that the Proterozoic igneous rocks do not include any significant contributions derived from the Archaean crust, and the chemistry of rocks, together with the isotope data, suggests that they were formed at a destructive plate margin. The Proterozoic rocks are found in a narrow zone (up to 30 km wide) between the Archaean gneisses to the north and south of Nordre Stroemfjord, and are interpreted as reflecting the existence of a suture between two Archaean continental blocks. Zircon U-Pb data and other isotope evidence show that subduction started before ca. 1920 Ma ago, and lasted until ca. 1850 Ma when collision occurred, with consequent crustal thickening, high-grade metamorphism and local anatexis. Given the time-span for the operation of subduction, the existence of a wide Nagssugtoqidian ocean can be inferred, even for slow rates of plate motion. (orig./SHOE)

  16. Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

    The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

  17. Isotopic evidence for residential mobility of farming communities during the transition to agriculture in Britain.

    Science.gov (United States)

    Neil, Samantha; Evans, Jane; Montgomery, Janet; Scarre, Chris

    2016-01-01

    Development of agriculture is often assumed to be accompanied by a decline in residential mobility, and sedentism is frequently proposed to provide the basis for economic intensification, population growth and increasing social complexity. In Britain, however, the nature of the agricultural transition (ca 4000 BC) and its effect on residence patterns has been intensely debated. Some authors attribute the transition to the arrival of populations who practised a system of sedentary intensive mixed farming similar to that of the very earliest agricultural regimes in central Europe, ca 5500 BC, with cultivation of crops in fixed plots and livestock keeping close to permanently occupied farmsteads. Others argue that local hunter-gatherers within Britain adopted selected elements of a farming economy and retained a mobile way of life. We use strontium and oxygen isotope analysis of tooth enamel from an Early Neolithic burial population in Gloucestershire, England, to evaluate the residence patterns of early farmers. Our results are consistent with the hypothesis that early farming communities in Britain were residentially mobile and were not fully sedentary. Results highlight the diverse nature of settlement strategies associated with early farming in Europe and are of wider significance to understanding the effect of the transition to agriculture on residence patterns.

  18. Glacial meltwater input to the Alaska Coastal Current: Evidence from oxygen isotope measurements

    Science.gov (United States)

    Kipphut, George W.

    1990-04-01

    Results of a study of the oxygen isotopic composition of coastal, pelagic, and fresh waters from the northern Gulf of Alaska region are presented. This study was undertaken to investigate whether isotopic tracers could be of use in determining the important freshwater inputs to the Alaska Coastal Current (ACC) and whether they could confirm the presence of the ACC in coastal waters west of Kodiak Island. The Alaska Coastal Current, the major coastal circulation feature of the northern Gulf of Alaska, can be distinguished from oceanic waters on the basis of its lower salinity at least as far west as Kodiak Island. This study adds significantly to the small amount of oxygen isotopic information available for the waters of this region. The isotopic results suggest that in late summer, glacial meltwater may provide a substantial portion of the total freshwater runoff into the ACC, and that the ACC does extend as far to the west as Unimak Pass.

  19. Barium isotopes in Allende meteorite - Evidence against an extinct superheavy element

    Science.gov (United States)

    Lewis, R. S.; Anders, E.; Shimamura, T.; Lugmair, G. W.

    1983-01-01

    Carbon and chromite fractions from the Allende meteorite that contain isotopically anomalous xenon-131 to xenon-136 (carbonaceous chondrite fission or CCF xenon) at up to 5 x 10 to the 11th atoms per gram show no detectable isotopic anomalies in barium-130 to barium-138. This rules out the possibility that the CCF xenon was formed by in situ fission of an extinct superheavy element. Apparently the CCF xenon and its carbonaceous carrier are relics from stellar nucleosynthesis.

  20. Ruthenium isotopic evidence for an inner Solar System origin of the late veneer.

    Science.gov (United States)

    Fischer-Gödde, Mario; Kleine, Thorsten

    2017-01-25

    The excess of highly siderophile elements in the Earth's mantle is thought to reflect the addition of primitive meteoritic material after core formation ceased. This 'late veneer' either comprises material remaining in the terrestrial planet region after the main stages of the Earth's accretion, or derives from more distant asteroidal or cometary sources. Distinguishing between these disparate origins is important because a late veneer consisting of carbonaceous chondrite-like asteroids or comets could be the principal source of the Earth's volatiles and water. Until now, however, a 'genetic' link between the late veneer and such volatile-rich materials has not been established or ruled out. Such genetic links can be determined using ruthenium (Ru) isotopes, because the Ru in the Earth's mantle predominantly derives from the late veneer, and because meteorites exhibit Ru isotope variations arising from the heterogeneous distribution of stellar-derived dust. Although Ru isotopic data and the correlation of Ru and molybdenum (Mo) isotope anomalies in meteorites were previously used to argue that the late veneer derives from the same type of inner Solar System material as do Earth's main building blocks, the Ru isotopic composition of carbonaceous chondrites has not been determined sufficiently well to rule them out as a source of the late veneer. Here we show that all chondrites, including carbonaceous chondrites, have Ru isotopic compositions distinct from that of the Earth's mantle. The Ru isotope anomalies increase from enstatite to ordinary to carbonaceous chondrites, demonstrating that material formed at greater heliocentric distance contains larger Ru isotope anomalies. Therefore, these data refute an outer Solar System origin for the late veneer and imply that the late veneer was not the primary source of volatiles and water on the Earth.

  1. Ruthenium isotopic evidence for an inner Solar System origin of the late veneer

    Science.gov (United States)

    Fischer-Gödde, Mario; Kleine, Thorsten

    2017-01-01

    The excess of highly siderophile elements in the Earth’s mantle is thought to reflect the addition of primitive meteoritic material after core formation ceased. This ‘late veneer’ either comprises material remaining in the terrestrial planet region after the main stages of the Earth’s accretion, or derives from more distant asteroidal or cometary sources. Distinguishing between these disparate origins is important because a late veneer consisting of carbonaceous chondrite-like asteroids or comets could be the principal source of the Earth’s volatiles and water. Until now, however, a ‘genetic’ link between the late veneer and such volatile-rich materials has not been established or ruled out. Such genetic links can be determined using ruthenium (Ru) isotopes, because the Ru in the Earth’s mantle predominantly derives from the late veneer, and because meteorites exhibit Ru isotope variations arising from the heterogeneous distribution of stellar-derived dust. Although Ru isotopic data and the correlation of Ru and molybdenum (Mo) isotope anomalies in meteorites were previously used to argue that the late veneer derives from the same type of inner Solar System material as do Earth’s main building blocks, the Ru isotopic composition of carbonaceous chondrites has not been determined sufficiently well to rule them out as a source of the late veneer. Here we show that all chondrites, including carbonaceous chondrites, have Ru isotopic compositions distinct from that of the Earth’s mantle. The Ru isotope anomalies increase from enstatite to ordinary to carbonaceous chondrites, demonstrating that material formed at greater heliocentric distance contains larger Ru isotope anomalies. Therefore, these data refute an outer Solar System origin for the late veneer and imply that the late veneer was not the primary source of volatiles and water on the Earth.

  2. Effects of isotope selection on solution convergence in HZE transport

    Science.gov (United States)

    Kim, Myung-Hee Y.; Wilson, John W.; Kiefer, Richard L.; Thibeault, Sheila A.

    1994-01-01

    A fragmenting iron ion produces hundreds of isotopes during nuclear reactions. These isotopes are represented in the solution of the transport problem. A reduced set of isotopes is selected to minimize the computational burden but introduces error in the final result. A minimum list of 122 isotopes is required for adequate representation of the mass and charge distributions of the secondary radiation fields. A reduced set of 80 isotopes is sufficient to represent the charge distribution alone and represents reasonably well the linear energy transfer properties of the iron beam. Because iron fragmentation produces nearly every isotope lighter than iron, the resulting 122-isotope list should be adequate for ion beams with charges equal to or less than 26.

  3. The effects of inhomogeneous isotope distribution on the vibrational properties of isotope enriched double walled carbon nanotubes

    International Nuclear Information System (INIS)

    Zolyomi, V.; Simon, F.; Rusznyak, A.; Kuerti, J.; Pfeiffer, R.; Peterlik, H.; Kuzmany, H.

    2007-01-01

    The radial breathing mode in the Raman spectrum of 13 C isotope enriched single walled carbon nanotubes is inhomogeneously broadened due to the random distribution of isotopes. We study this effect theoretically using density functional theory within the local density approximation and compare the result with experiments on isotope engineered double walled carbon nanotubes in which the inner tubes were grown from a mixture of 13 C enriched fullerenes and natural fullerenes. As explained by the calculations, this synthesis procedure leads to an increased inhomogeneity compared to a case when only enriched fullerenes are used. The good agreement between the measurements and calculations shows the absence of carbon diffusion along the tube axis during inner tube growth, and presents a strong support of the theory that inner tube growth is governed by Stone-Wales transformations following the interconnection of fullerenes. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Mesoproterozoic juvenile crust in microcontinents of the Central Asian Orogenic Belt: evidence from oxygen and hafnium isotopes in zircon.

    Science.gov (United States)

    He, Zhen-Yu; Klemd, Reiner; Yan, Li-Li; Lu, Tian-Yu; Zhang, Ze-Ming

    2018-03-22

    We report in situ O and Hf isotope data of zircon grains from coeval Mesoproterozoic (ca. 1.4 Ga) igneous metamafic (amphibolite) and granitic rocks of the Chinese Central Tianshan microcontinent (CTM) in the southern Central Asian Orogenic Belt (CAOB). Zircon grains from amphibolite have mantle-like δ 18 O VSMOW values of 4.7-5.6‰ and juvenile Hf isotopic compositions (ε Hf (t) = 8.4-15.3; T DMC  = 1.57-1.22 Ga), whereas those from granitic rocks have δ 18 O VSMOW values of 5.6-7.0‰ and evolved Hf isotopic compositions (ε Hf (t) = -1.0-8.2; T DMC  = 2.09-1.62 Ga). Zircon O-Hf isotopic compositions of the metamafic and granitic rocks provide evidence for Mesoproterozoic (ca. 1.4 Ga) crustal growth and a substantial Palaeoproterozoic supracrustal component in the CTM. These findings and previous studies, reporting ca. 1.4 Ga magmatic rocks from other microcontinents of the CAOB, suggest that a large belt of Mesoproterozoic (ca. 1.4 Ga) juvenile continental crust formed in a continental terrane, fragments of which now occur over a distance of more than a thousand kilometres in the southern CAOB.

  5. Lithium isotope evidence for subduction-enriched mantle in the source of mid-ocean-ridge basalts.

    Science.gov (United States)

    Elliott, Tim; Thomas, Alex; Jeffcoate, Alistair; Niu, Yaoling

    2006-10-05

    'Recycled' crustal materials, returned from the Earth's surface to the mantle by subduction, have long been invoked to explain compositional heterogeneity in the upper mantle. Yet increasingly, problems have been noted with this model. The debate can be definitively addressed using stable isotope ratios, which should only significantly vary in primitive, mantle-derived materials as a consequence of recycling. Here we present data showing a notable range in lithium isotope ratios in basalts from the East Pacific Rise, which correlate with traditional indices of mantle heterogeneity (for example, 143Nd/144Nd ratios). Such co-variations of stable and radiogenic isotopes in melts from a normal ridge segment provide critical evidence for the importance of recycled material in generating chemical heterogeneity in the upper mantle. Contrary to many models, however, the elevated lithium isotope ratios of the 'enriched' East Pacific Rise lavas imply that subducted ocean crust is not the agent of enrichment. Instead, we suggest that fluid-modified mantle, which is enriched during residency in a subduction zone, is mixed back into the upper mantle to cause compositional variability.

  6. 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...

  7. Charge exchange effect on laser isotope separation of atomic uranium

    International Nuclear Information System (INIS)

    Niki, Hideaki; Izawa, Yasukazu; Otani, Hiroyasu; Yamanaka, Chiyoe

    1982-01-01

    Uranium isotope separating experiment was performed using the two-step photoionization technique with dye laser and nitrogen laser by heating uranium metal with electron beam and producing atomic beam using generated vapour. The experimental results are described after explaining the two-step photoionization by laser, experimental apparatus, the selection of exciting wavelength and others. Enrichment factor depends largely on the spectrum purity of dye laser which is the exciting source. A large enrichment factor of 48.3 times was obtained for spectrum width 0.03A. To put the uranium isotope separation with laser into practice, the increase of uranium atomic density is considered to be necessary for improving the yield. Experimental investigation was first carried out on the charge exchange effect that seems most likely to affect the decrease of enrichment factor, and the charge exchange cross-section was determined. The charge exchange cross-section depends on the relative kinetic energy between ions and atoms. The experimental result showed that the cross-section was about 5 x 10 -13 cm 2 at 1 eV and 10 -13 cm 2 at 90 eV. These values are roughly ten times as great as those calculated in Lawrence Livermore Laboratory, and it is expected that they become the greatest factor for giving the upper limit of uranium atomic density in a process of practical application. (Wakatsuki, Y.)

  8. Ionic conductivity in aqueous solutions: deuterium isotope effect

    International Nuclear Information System (INIS)

    Samanta, Alok; Ghosh, Swapan K.

    1997-01-01

    A simple theoretical investigation of the calculation of ionic conductivity in aqueous solution is presented. The dipolar hard sphere model for the solvent which has been successful elsewhere has been employed here and it has been possible to reproduce the experimental results quite accurately for both water and heavy water using only two parameters. In a more detailed theoretical approach one should employ better models for water with proper account of its vibrations, liberations and also hydrogen bonding. It is also of interest to study the temperature effect and the concentration dependence of the conductivity. The time-dependent friction can also be calculated from the present formalism and be used for the study of isotope effect in proton transfer reactions or other aspects of chemical dynamics

  9. Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model

    Science.gov (United States)

    Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.; Otto-Bliesner, Bette L.; Marcott, Shaun A.; Zhang, Jiaxu; Wang, Xianfeng; Nusbaumer, Jesse; Wong, Tony E.; Jahn, Alexandra; Noone, David

    2017-12-01

    Variations in terrestrial oxygen-isotope reconstructions from ice cores and speleothems have been primarily attributed to climatic changes of surface air temperature, precipitation amount, or atmospheric circulation. Here we demonstrate with the fully coupled isotope-enabled Community Earth System Model an additional process contributing to the oxygen-isotope variations during glacial meltwater events. This process, termed "the direct meltwater effect," involves propagating large amounts of isotopically depleted meltwater throughout the hydrological cycle and is independent of climatic changes. We find that the direct meltwater effect can make up 15-35% of the δ18O signals in precipitation over Greenland and eastern Brazil for large freshwater forcings (0.25-0.50 sverdrup (106 m3/s)). Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of the freshwater forcing and is sensitive to both the location and shape of the meltwater. These new modeling results have important implications for past climate interpretations of δ18O.

  10. Isotope separation

    International Nuclear Information System (INIS)

    Ravoire, Jean

    1978-11-01

    Separation of isotopes is treated in a general way, with special reference to the production of enriched uranium. Uses of separated isotopes are presented quickly. Then basic definitions and theoretical concepts are explained: isotopic effects, non statistical and statistical processes, reversible and irreversible processes, separation factor, enrichment, cascades, isotopic separative work, thermodynamics. Afterwards the main processes and productions are reviewed. Finally the economical and industrial aspects of uranium enrichment are resumed [fr

  11. The isotope altitude effect reflected in groundwater: a case study from Slovenia.

    Science.gov (United States)

    Mezga, Kim; Urbanc, Janko; Cerar, Sonja

    2014-01-01

    This paper presents the stable isotope data of oxygen (δ(18)O) and hydrogen (δ(2)H) in groundwater from 83 sampling locations in Slovenia and their interpretation. The isotopic composition of water was monitored over 3 years (2009-2011), and each location was sampled twice. New findings on the isotopic composition of sampled groundwater are presented, and the data are also compared to past studies regarding the isotopic composition of precipitation, surface water, and groundwater in Slovenia. This study comprises: (1) the general characteristics of the isotopic composition of oxygen and hydrogen in groundwater in Slovenia, (2) the spatial distribution of oxygen isotope composition (δ(18)O) and d-excess in groundwater, (3) the groundwater isotope altitude effect, (4) the correlation between groundwater d-excess and the recharge area altitude of the sampling location, (5) the relation between hydrogen and oxygen isotopes in groundwater in comparison to the global precipitation isotope data, (6) the groundwater isotope effect of distance from the sea, and (7) the estimated relation between the mean temperature of recharge area and δ(18)O in groundwater.

  12. Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: Resolving theory and experiments

    International Nuclear Information System (INIS)

    Cole, Amanda S.; Boering, Kristie A.

    2006-01-01

    In addition to the anomalous 17 O and 18 O isotope effects in the three-body ozone formation reaction O+O 2 +M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or 'non-mass-dependent'), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in 17 O and 18 O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O( 1 D), O( 3 P), O 2 ( 1 Δ), and O 2 ( 1 Σ) is needed through experiments we suggest here

  13. Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ13C and δ15N

    Directory of Open Access Journals (Sweden)

    Christopher D. Stallings

    2015-03-01

    and corresponding low levels of mass loss with a substantial change in the isotope value of the sample. Regardless of mechanism, it was evident that accounting for offsets caused by different preservation methods was not possible using the standard correction. Caution is warranted when interpreting the results from specimens stored in either ethanol or salt, especially when using those from multiple preservation techniques. We suggest the use of ice as the preferred preservation technique for muscle tissue when conducting stable isotope analysis as it is widely available, inexpensive, easy to transport and did not impart a significant offset in measured isotopic values. Our results provide additional evidence that preservation effects on stable isotope analysis can be highly contextual, thus requiring their effects to be measured and understood for each species and isotopic ratio of interest before addressing research questions.

  14. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

    Science.gov (United States)

    Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J

    2012-05-30

    Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate

  15. The behavior of lithium and its isotopes in oilfield brines: evidence from the Heletz-Kokhav field, Israel

    Science.gov (United States)

    Chan, Lui-Heung; Starinsky, Abraham; Katz, Amitai

    2002-02-01

    Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ 6Li notation, vary from -26.3 to -17.9‰, all values being significantly higher than that of modern seawater (-32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ 6Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.

  16. Variation in dietary histories among the immigrants of Machu Picchu: Carbon and nitrogen isotope evidence

    International Nuclear Information System (INIS)

    Turner, Bethany L; Kingston, John D; Armelagos, George J

    2010-01-01

    This study estimates dietary composition during infancy and childhood among 71 adults interred at the site of Machu Picchu, a royal Inca estate in the southern highlands of Peru. Recent research suggests that the majority of individuals were members of the cosmopolitan yana and aclla servant classes, and immigrated to the site from different regions; individual dietary histories may have been similarly varied. Diet was estimated at multiple points in early life through characterization of carbon and nitrogen isotope ratios in tooth enamel and dentin, which preserve isotopic values from the first years of life. These data were compared to isotopic data from modern food samples, and analyzed using recently-published statistical models. A subset of individuals also has existing bone collagen isotopic data, which reflects diet from the last decade of life and thus permits comparison over the life course. Results indicate significant variation in enamel δ 13 C (approximately 12% o ), dentin δ 13 C (approximately 9% o ) and δ 15 N (approximately 8% o ) between individuals across the study population. These findings suggest substantial variability in diet during infancy and childhood, and support interpretations that this population was primarily yanacona or mixed yanaconalacllacona. This study also highlights the utility of multi-tissue isotopic analysis in more nuanced reconstruction of diet in the ancient Andes

  17. Enrichment and separation of isotopes utilizing a novel magnetic isotope effect. Final report

    International Nuclear Information System (INIS)

    Chung, C.J.; Turro, N.J.; Ruderman, W.

    1983-04-01

    Results are presented of a study undertaken to find a suitable isotope separation process for the 13 C- 12 C system that could be adapted to a multi-stage process for the commercial enrichment and separation of isotopes. Experiments reveal that solid porous silica provides an appropriate medium for the efficient enrichment of 13 C via the photolysis of dibenzyl ketones (and related ketones). It is concluded that a system can be designed for the practical separation of 13 C from 12 C based on the photolysis in a magnetic field of ketones absorbed on solid porous silica

  18. Estuarine fish health assessment: Evidence of wastewater impacts based on nitrogen isotopes and histopathology

    Energy Technology Data Exchange (ETDEWEB)

    Schlacher, Thomas A. [Faculty of Science, Health and Education, University of the Sunshine Coast, Maroochydore DC, QLD 4558 (Australia)], E-mail: tschlach@usc.edu.au; Mondon, Julie A. [School of Life and Environmental Sciences, Deakin University, Warrnambool (Australia)], E-mail: julie.mondon@deakin.edu.au; Connolly, Rod M. [Australian Rivers Institute - Coast and Estuaries and Griffith School of Environment, Griffith University (Australia)], E-mail: r.connolly@griffith.edu.au

    2007-11-15

    Sewage effluent is a powerful agent of ecological change in estuaries. While the effects of sewage pollution on water quality are usually well documented, biological responses of exposed organisms are not. We quantified health impacts in the form of pathological tissue changes across multiple organs in estuarine fish exposed to elevated levels of treated wastewater. Structural pathologies were compared in wild populations of four fish species from two subtropical estuaries on the east coast of Australia that differ substantially in the amount of direct wastewater loadings. Uptake of sewage-derived nitrogen by fish was traced with stable nitrogen isotopes. Pathologies were common in the liver, spleen, gill, kidney and muscle tissues, and included granulomas, melanomacrophage aggregates, and multiple deformities of the gill epithelia. Tissue deformities were more frequent in fish exposed directly to wastewater discharges. Mullet (Valamugil georgii) were most affected, with only a single specimen free of pathologies in the sewage-impacted estuary. Similarly, in those fish that had structural abnormalities, more deformities were generally found in individuals from sites receiving sewage. These spatial contrasts in impaired fish health correspond to significantly enriched {delta}{sup 15}N values in fish muscle as a consequence of fish assimilating sewage-N. Overall, the pattern of lower health and enriched {delta}{sup 15}N values in fish from sewage-impacted areas suggests that organism health is lowered by sewage inputs to estuaries. Measurements of organism health are required to understand the effects of sewage on estuarine ecosystems, and histopathology of fishes is a powerful tool to achieve this.

  19. Isotopic modeling of the sub-cloud evaporation effect in precipitation.

    Science.gov (United States)

    Salamalikis, V; Argiriou, A A; Dotsika, E

    2016-02-15

    In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a 'heat capacity' model providing high correlation coefficients for both isotopes (R(2)>80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH=95%) sub-cloud evaporation is negligible and the isotopic

  20. Moisture source in the Hyblean Mountains region (south-eastern Sicily, Italy): Evidence from stable isotopes signature

    International Nuclear Information System (INIS)

    Grassa, Fausto; Favara, Rocco; Valenza, Mariano

    2006-01-01

    Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line (δD = 6.50 δ 18 O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average 2 H excess value of +21.2 per mille was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and 18 O/ 16 O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the δ 18 O vs δD relationship for Hyblean groundwater is δD = 4.85 δ 18 O-2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes

  1. Moisture source in the Hyblean Mountains region (south-eastern Sicily, Italy): Evidence from stable isotopes signature

    Energy Technology Data Exchange (ETDEWEB)

    Grassa, Fausto [Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Palermo, Via Ugo La Malfa, 153, 90146 Palermo (Italy)]. E-mail: f.grassa@pa.ingv.it; Favara, Rocco [Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Palermo, Via Ugo La Malfa, 153, 90146 Palermo (Italy); Valenza, Mariano [Dipartimento CFTA, Universita di Palermo, Palermo, Via Archirafi, 36, 90123, Palermo (Italy)

    2006-12-15

    Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line ({delta}D = 6.50 {delta} {sup 18}O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average {sup 2}H excess value of +21.2 per mille was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and {sup 18}O/{sup 16}O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the {delta} {sup 18}O vs {delta}D relationship for Hyblean groundwater is {delta}D = 4.85 {delta} {sup 18}O-2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes.

  2. Hf Isotope Evidence for Subducted Basalt and Sediment Contributions to the Eastern Trans-Mexican Volcanic Belt

    Science.gov (United States)

    Cai, Y.; Tuena, A. G.; Capra, L.; Straub, S. M.; Goldstein, S. L.; Langmuir, C. H.

    2005-12-01

    Magmas generated at thick crust continental arcs often have enriched continental crust-like trace element patterns and Pb-Sr-Nd isotope ratios that are intermediate to both upper mantle and crustal compositions. Thus it is difficult to distinguish between contributions from (a) the subducted basalt and the upper mantle wedge, and (b) subducted sediment and the continental crust. These issues have been the focus of major controversy. Here we show evidence for subduction contributions to lavas in a classic thick crust environment. In Eastern Trans-Mexican Volcanic Belt, the upper continental crust is 30 km to 45 km thick. However, primitive mafic lavas erupt on many sites across the arc. We have analyzed the subducting sediments as represented by DSDP 487, located seaward of the trench, where the lower third of the sediment column has strongly hydrothermal pelagic features and the upper two-thirds is composed of terrigenous sediments. The pelagic sediments have distinctive features that could be used to identify a subduction component in the volcanics, including high REE/Hf, negative Ce anomalies, and Nd-Hf isotopes that lie on the "seawater array" and offset from the "mantle-crust" array. We have focused on a unique series of lavas from volcano Nevado de Toluca, located southwest of Mexico City. These lavas show negative Ce anomalies coupled with low REE/Hf and Zr/Nd ratios. Hf-Nd isotope ratios show a shallow trend compared to the mantle-crust array, consistent with a pelagic component. In addition, Hf isotopes show a striking positive correlation with Ce anomalies that trend toward the pelagic sediment compositions. These and other observations provide clear evidence for a component from subducted sediment in the lavas. In addition, there is a negative correlation of Lu/Hf and Hf isotopes that requires a mixing endmember with MORB-like Hf isotope ratios but with lower than MORB Lu/Hf. This indicates a melt from eclogitic subducted basalt. Compared to other

  3. Isotopic equilibrium between precipitation and water vapor: evidence from continental rains in central Kenya

    Science.gov (United States)

    Soderberg, K.; Gerlein, C.; Kemeny, P. C.; Caylor, K. K.

    2013-12-01

    An accurate understanding of the relationships between the isotopic composition of liquid water and that of water vapor in the environment can help describe hydrologic processes across many scales. One such relationship is the isotopic equilibrium between falling raindrops and the surrounding vapor. The degree of equilibration is used to model the isotopic composition of precipitation in isotope-enable general circulation models and land-atmosphere exchange models. Although this equilibrium has been a topic of isotope hydrology research for more than four decades, few studies have included vapor measurements to validate modeling efforts. Recent advances in laser technology have allowed for in situ vapor measurements at high temporal resolution (e.g., >1 Hz). Here we present concomitant rain and vapor measurements for a series of 17 rain events during the 'Continental' rainy season (June through August) at Mpala Research Center in central Kenya. Rain samples (n=218) were collected at intervals of 2 to 35 minutes (median of 3 minutes) depending on the rain rate (0.4 to 10.5 mm/hr). The volume-weighted mean rain values for δ18O, δ2H and D-excess (δ2H - 8* δ18O) were 0.1 ‰, 10.7 ‰, and 10.1 ‰. These values are more enriched than the annual weighted means reported for the area (-2.2 ‰, -7.6 ‰, and 11.0 ‰, respectively). Vapor was measured continuously at ~2Hz (DLT-100, Los Gatos Research), with an inverted funnel intake 4m above the ground surface. The mean vapor isotopic composition during the rain events was -10.0 +/- 1.2 ‰ (1 σ) for δ18O and -73.9 +/- 7.0 ‰ for δ2H. The difference between the rain sample isotopic composition and that of liquid in isotopic equilibrium with the corresponding vapor at the ambient temperature was 0.8 +/- 2.2 ‰ for δ18O and 6.2 +/- 7.0 ‰ for δ2H. This disequilibrium was found to correlate with the natural log of rain rate (R2 of 0.26 for δ18O and 0.46 for δ2H), with lower rain rates having larger

  4. Stable isotope evidence of long-term changes in North Sea food web structure

    DEFF Research Database (Denmark)

    Richardson, Katherine; Christensen, Jens Tang

    2008-01-01

    coast. Porpoises collected after ~1960 had significantly lower d15N than porpoises collected earlier. This change in d15N implies that fundamental changes in food web structure in, or nutrient availability to, the North Sea have taken place over the last ~150 yr and that most of the change occurred over...... reported here may be a reflection of a change in the isotope signature of nitrogen entering the food web. Regardless of its underlying cause, the recorded change in isotopic signature in harbour porpoises is noteworthy as it represents the first fisheries-independent documentation of a long-term temporal...

  5. Magnetic isotope effect of magnesium in phosphoglycerate kinase phosphorylation.

    Science.gov (United States)

    Buchachenko, Anatoly L; Kouznetsov, Dmitri A; Orlova, Marina A; Markarian, Artyom A

    2005-08-02

    Phosphoglycerate kinase (PGK) is found to be controlled by a (25)Mg(2+)-related magnetic isotope effect. Mg(2+) nuclear spin selectivity manifests itself in PGK-directed ADP phosphorylation, which has been clearly proven by comparison of ATP synthesis rates estimated in reaction mixtures with different Mg isotopy parameters. Both pure (25)Mg(2+) (nuclear spin 5/2, magnetic moment +0.85) and (24)Mg(2+) (spinless, nonmagnetic nucleus) species as well as their mixtures were used in experiments. In the presence of (25)Mg(2+), ATP production is 2.6 times higher compared with the yield of ATP reached in (24)Mg(2+)-containing PGK-based catalytic systems. The chemical mechanism of this phenomenon is discussed. A key element of the mechanism proposed is a nonradical pair formation in which (25)Mg(+) radical cation and phosphate oxyradical are involved.

  6. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a Grignard reagent to methyl iodide, and for reduction of methyl iodide with tributyltin hydride or with gaseous hydrogen iodide. Very small KIE's were found for electron transfer to methyl iodide from magnesium in ether or from sodium in ammonia. The reason may be that these reactions are transport......a-Deuterium kinetic isotope effects (KIE's) have been determined for the reaction of methyl iodide with a series of reducing agents. Reagents which transfer hydride ion in an SN2 reaction show small inverse or small normal KIE's. Reagents which transfer an electron to methyl iodide to produce...... methyl radical show large normal KIE's up to 20 % per a-D. Large KIE's were found for the reaction of methyl iodide with sodium, for Pd-catalyzed reaction of methyl iodide with hydrogen, for ET at a platinum cathode, for ET from benzophenone ketyl or from sodium naphthalenide, for iron catalyzed ET from...

  7. Research of biological isotope effect of deuterium in Anabaena azollae

    International Nuclear Information System (INIS)

    Zhang Yongbo; Wang Wenqing; Shi Dingji; Luo Shanggeng

    1996-01-01

    Anabaena azollae is cultured in BG-11 medium whose mass fraction of heavy water is 0%, 10%, 30%, 60% and 90%, respectively. During different time, activities of photosynthesis, respiration and nitrogenase are measured. In addition, growth-curve, absorption spectrum and low temperature fluorescence spectrum are given. The change of cellular morphology is observed with scanning electron microscope. The results show that the addition of heavy water causes lagging of the exponential period of growth, and inhibits the activities of photosynthesis respiration and nitrogenase markedly. Absorption spectrum shows that the ratio of phycobilins to carotenoid decreases with increasing percentage of heavy water. Low temperature fluorescence spectrum indicates that the ratio of F 733 /F 695 decreases and photo-energy distributed to system II is more than to system I. According to the maximum of net photosynthesis, the isotope effect is also discussed

  8. Effect of density of state on isotope effect exponent of two-band superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Kumvongsa, C.; Burakorn, A.; Changkanarth, P.; Yoksan, S.

    2005-01-01

    The exact formula of T c 's equation and the isotope effect exponent of two-band s-wave superconductors in weak-coupling limit are derived by considering the influence of two kinds of density of state: constant and van Hove singularity. The paring interaction in each band consisted of two parts: the electron-phonon interaction and non-electron-phonon interaction are included in our model. We find that the interband interaction of electron-phonon show more effect on isotope exponent than the intraband interaction and the isotope effect exponent with constant density of state can fit to experimental data, MgB 2 and high-T c superconductor, better than van Hove singularity density of state

  9. Effect of Nutrient-limitation on the Microbial S-isotope Fractionation

    Science.gov (United States)

    Sim, M.; Bosak, T.; Ono, S.

    2011-12-01

    Microbial sulfate reduction (MSR) utilizes sulfate as an electron acceptor and produces sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. This process controls much of the distribution of sulfur isotopes in sedimentary sulfides and sulfates, but the magnitude of S-isotope fractionations in natural environments often exceeds those in laboratory cultures. This difference may be due to many factors and environmental stresses, including the limitation by essential nutrients. However, none of the studies to date investigated the effect of nutrients such as nitrogen, iron, or phosphate, on sulfur isotope fractionation by sulfate reducing microbes. Here, we examine the influence of N and Fe limitation on multiple-S isotope fractionation by a marine sulfate reducing bacterium by reducing the concentrations of N and Fe in a defined medium by 10 to 1000 times. Nitrogen limitation reduces the growth rate and the cellular yield, but increases the respiration rate without altering the magnitude of isotope fractionation. In contrast, S-isotope fractionation was up to 40% larger in iron-limited than in iron-replete cultures. This increase in sulfur isotope fractionation is accompanied by a decrease in the growth rate, the cellular yield, the respiration rate, and the cytochrome c content. Thus, iron limitation increases the reversibility of microbial sulfate reduction pathway, possibly by affecting iron-containing respiratory complexes such as cytochromes and iron-sulfur proteins. The apparent influence of iron limitation on S-isotope fractionation is relevant to the interpretations of sulfur isotope data in modern and ancient environments. Some areas where iron limitation may lead to large observed S-isotope effects include iron-limited deep open ocean sediments, whereas smaller S-isotope effects would be expected where Fe is more bioavailable (e.g., in anoxic basins, where Fe enrichment occurs due to Fe shuttling).

  10. No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

    Science.gov (United States)

    Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming

    2012-10-01

    In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for

  11. Investigation of the enzymatic mechanism of yeast orotidine-5'-monophosphate decarboxylase using 13C kinetic isotope effects

    International Nuclear Information System (INIS)

    Smiley, J.A.; Bell, J.B.; Jones, M.E.; Paneth, P.; O'Leary, M.H.

    1991-01-01

    Orotidine-5'-monophosphate decarboxylase (ODCase) from Saccharomyces cerevisiae displays an observed 13 C kinetic isotope effect of 1.0247 ± 0.0008 at 25 C, pH 6.8. The observed isotope effect is sensitive to changes in the reaction medium, such as pH, temperature, or glycerol content. The value of 1.0494 ± 0.0006 measured at pH 4.0, 25 C, is not altered significantly by temperature or glycerol, and thus the intrinsic isotope effect for the reaction is apparently being observed under these conditions and decarboxylation is almost entirely rate-determining. These data require a catalytic mechanism with freely reversible binding and one in which a very limited contribution to the overall rate is made by chemical steps preceding decarboxylation; the zwitterion mechanism of Beak and Siegel, which involves only protonation of the pyrimidine ring, is such a mechanism. With use of an intrinsic isotope effect of 1.05, a partitioning factor of less than unity is calculated for ODCase at pH 6.0, 25 C. A quantitative kinetic analysis using this result excludes the possibility of an enzymatic mechanism involving covalent attachment of an enzyme nucleophile to C-5 of the pyrimidine ring. These data fit a kinetic model in which an enzyme proton necessary for catalysis is titrated at high pH, thus providing evidence for the catalytic mechanism of Beak and Siegal

  12. Isotope effect and deuterium excess parameter revolution in ice and snow melt

    International Nuclear Information System (INIS)

    Yin Guan; Ni Shijun; Fan Xiao; Wu Hao

    2003-01-01

    The change of water isotope composition actually is a integrated reaction depending on the change of environment. The ice and snow melt of different seasons in high mountain can obviously influence the change of isotope composition and deuterium excess parameter of surface flow and shallow groundwater. To know the isotopic fractionation caused by this special natural background, explore its forming and evolvement, is unusually important for estimating, the relationship between the environment, climate and water resources in an area. Taking the example of isotope composition of surface flow and shallow groundwater in Daocheng, Sichuan, this paper mainly introduced the changing law of isotope composition and deuterium excess parameter of surface flow and hot-spring on conditions of ice and snow melt with different seasons in high mountain; emphatically discussed the isotope effect and deuterium excess parameter revolution in the process of ice and snow melting and its reason. (authors)

  13. Lead isotope evidence for a young formation age of the Earth-Moon system

    Science.gov (United States)

    Connelly, J. N.; Bizzarro, M.

    2016-10-01

    A model of a giant impact between two planetary bodies is widely accepted to account for the Earth-Moon system. Despite the importance of this event for understanding early Earth evolution and the inventory of Earth's volatiles critical to life, the timing of the impact is poorly constrained. We explore a data-based, two-stage Pb isotope evolution model in which the timing of the loss of volatile Pb relative to refractory U in the aftermath of the giant impact is faithfully recorded in the Pb isotopes of bulk silicate Earth. Constraining the first stage Pb isotopic evolution permits calculating an age range of 4.426-4.417 Ga for the inflection in the U/Pb ratio related to the giant impact. This model is supported by Pb isotope data for angrite meteorites that we use to demonstrate volatility-driven, planetary-scale Pb loss was an efficient process during the early Solar System. The revised age is ∼100 Myr younger than most current estimates for the age of the Moon but fully consistent with recent ages for lunar ferroan anorthosite and the timing of Earth's first crust inferred from the terrestrial zircon record. The estimated loss of ∼98% of terrestrial Pb relative to the Solar System bulk composition by the end of the Moon-forming process implies that the current inventory of Earth's most volatile elements, including water, arrived during post-impact veneering by volatile-rich bodies.

  14. Scavenging of oxygen vacancies at modulation-doped oxide interfaces: Evidence from oxygen isotope tracing

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Döbeli, M.; Pomjakushina, E.

    2017-01-01

    , the mechanisms underlying the extreme mobility enhancement remain elusive. Herein, we used 18O isotope exchanged SrTi18O3 as substrates to create 2DEG at room temperature with and without the LSMO buffer layer. By mapping the oxygen profile across the interface between STO18 and disordered LaAlO3 or yttria...

  15. Evidence of isotopic fractionation of natural uranium in cultured human cells

    Science.gov (United States)

    Paredes, Eduardo; Avazeri, Emilie; Malard, Véronique; Vidaud, Claude; Reiller, Pascal E.; Ortega, Richard; Nonell, Anthony; Isnard, Hélène; Chartier, Frédéric; Bresson, Carole

    2016-12-01

    The study of the isotopic fractionation of endogen elements and toxic heavy metals in living organisms for biomedical applications, and for metabolic and toxicological studies, is a cutting-edge research topic. This paper shows that human neuroblastoma cells incorporated small amounts of uranium (U) after exposure to 10 µM natural U, with preferential uptake of the 235U isotope with regard to 238U. Efforts were made to develop and then validate a procedure for highly accurate n(238U)/n(235U) determinations in microsamples of cells. We found that intracellular U is enriched in 235U by 0.38 ± 0.13‰ (2σ, n = 7) relative to the exposure solutions. These in vitro experiments provide clues for the identification of biological processes responsible for uranium isotopic fractionation and link them to potential U incorporation pathways into neuronal cells. Suggested incorporation processes are a kinetically controlled process, such as facilitated transmembrane diffusion, and the uptake through a high-affinity uranium transport protein involving the modification of the uranyl (UO22+) coordination sphere. These findings open perspectives on the use of isotopic fractionation of metals in cellular models, offering a probe to track uptake/transport pathways and to help decipher associated cellular metabolic processes.

  16. Stable isotope evidence of food web connectivity by a top predatory ...

    African Journals Online (AJOL)

    In this study, food web connectivity within the Kowie Estuary on the south-east coast of South Africa was evidenced by the trophic behaviour of the predominantly piscivorous Argyrosomus japonicus. We examined stable isotopes of carbon (δ 13C) and nitrogen (δ 15N) in the dominant consumers (zooplankton, invertebrates ...

  17. Moulting and wintering grounds of Marsh Warblers Acrocephalus palustris: evidence from stable isotopes and ring recoveries

    Czech Academy of Sciences Publication Activity Database

    Procházka, Petr; Kralj, J.; Pearson, D. J.; Yohannes, E.

    2014-01-01

    Roč. 49, č. 2 (2014), s. 193-200 ISSN 0001-6454 R&D Projects: GA ČR GA13-06451S Institutional support: RVO:68081766 Keywords : bird migration * feather stable isotopes * ring recoveries * stopover * migratory connectivity * δ13C * δ15N Subject RIV: EG - Zoology Impact factor: 0.745, year: 2014

  18. Migratory connectivity in the Rusty Blackbird: Isotopic evidence from feathers of historical and contemporary specimens

    Science.gov (United States)

    Keith A. Hobson; Russell Greenberg; Steven L. Van Wilgenburg; Claudia. Mettke-Hofmann

    2010-01-01

    The Rusty Blackbird (Euphagus carolinus) has declined dramatically across its range in North America since at least the 1960s, but the causes for this decline are unknown. We measured ratios of stable hydrogen isotopes (δD) in feathers collected from Rusty Blackbirds wintering in the Mississippi Alluvial Valley (n = 255 birds) and the coastal plain of South Carolina...

  19. Tracing subducted sediment inputs to the Ryukyu arc-Okinawa Trough system: Evidence from thallium isotopes

    Science.gov (United States)

    Shu, Yunchao; Nielsen, Sune G.; Zeng, Zhigang; Shinjo, Ryuichi; Blusztajn, Jerzy; Wang, Xiaoyuan; Chen, Shuai

    2017-11-01

    Sediments are actively subducted in virtually every arc worldwide. However, quantifying their contributions to arc lavas and thereby establishing budgets of how sediments participate in slab-mantle interaction is challenging. In this contribution we use thallium (Tl) abundances and isotopic compositions of lavas from the Ryukyu arc (including south Kyushu) and its back-arc basin, Okinawa Trough, to investigate the influence of sediments from arc to back-arc. We also present extensive geochemical data for sediments and altered oceanic crust (AOC) outboard of the northern (DSDP Sites 296, 442B, 443 and 444) and central (DSDP Sites 294 and 295) part of the Ryukyu arc. The Tl isotopic compositions of sediments change systematically from lighter outboard of northern Ryukyu arc to heavier outboard of central Ryukyu arc. The feature reflects the dominance of terrigenous material and pelagic sedimentation outboard of the northern and central Ryukyu arc, respectively. Central and northern sections of Ryukyu arc and Okinawa Trough display larger range of Tl isotopic variation than southern section, which is consistent with more pelagic provenance for sediments outboard of central and northern Ryukyu arcs than that of expected sediments outboard of southern Ryukyu arc. Identical Tl, Sr, Nd and Pb isotope variations are found when comparing arc and back arc lavas, which indicates that sediments fluxes also account for the Tl isotopic variations in the Okinawa Trough lavas. Two-end-member mixing models of Tl with Pb, Sr and Nd isotopes require sediment inputs ofOkinawa Trough. Bulk mixing between mantle and sediment end members predict very similar sediment fluxes when using Tl, Sr, Nd and Pb isotopes, which indicates that fractionation of these elements must have happened after mixing between mantle and sediments. This conclusion is corroborated by model calculations of mixing between sediment melts with fractionated Sr/Nd ratios and mantle wedge, which show that no arc lava

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

    Science.gov (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

    2016-04-01

    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

  1. Gallium isotopic evidence for the fate of moderately volatile elements in planetary bodies and refractory inclusions

    Science.gov (United States)

    Kato, Chizu; Moynier, Frédéric

    2017-12-01

    The abundance of moderately volatile elements, such as Zn and Ga, show variable depletion relative to CI between the Earth and primitive meteorite (chondrites) parent bodies. Furthermore, the first solar system solids, the calcium-aluminum-rich inclusions (CAIs), are surprisingly rich in volatile element considering that they formed under high temperatures. Here, we report the Ga elemental and isotopic composition of a wide variety of chondrites along with five individual CAIs to understand the origin of the volatile elements and to further characterize the enrichment of the volatile elements in high temperature condensates. The δ71Ga (permil deviation of the 71Ga/69Ga ratio from the Ga IPGP standard) of carbonaceous chondrites decreases in the order of CI >CM >CO >CV and is inversely correlated with the Al/Ga ratio. This implies that the Ga budget of the carbonaceous chondrites parent bodies were inherited from a two component mixing of a volatile rich reservoir enriched in heavy isotope of Ga and a volatile poor reservoir enriched in light isotope of Ga. Calcium-aluminum-rich inclusions are enriched in Ga and Zn compared to the bulk meteorite and are both highly isotopically fractionated with δ71Ga down to -3.56‰ and δ66Zn down to -0.74‰. The large enrichment in the light isotopes of Ga and Zn in the CAIs implies that the moderately volatile elements were introduced in the CAIs during condensation in the solar nebula as opposed to secondary processing in the meteorite parent body and supports a change in gas composition in which CAIs were formed.

  2. Trans-Atlantic slavery: isotopic evidence for forced migration to Barbados.

    Science.gov (United States)

    Schroeder, Hannes; O'Connell, Tamsin C; Evans, Jane A; Shuler, Kristrina A; Hedges, Robert E M

    2009-08-01

    The question of the ultimate origin of African slaves is one of the most perplexing in the history of trans-Atlantic slavery. Here we present the results of a small, preliminary isotopic study that was conducted in order to determine the geographical origin of 25 enslaved Africans who were buried at the Newton plantation, Barbados, sometime between the late 17th and early 19th century. In order to gain a more nuanced understanding of the slaves' origin, we used a combination of carbon, nitrogen, oxygen, and strontium isotope analyses. Carbon and nitrogen isotope ratios were determined in bone and dentinal collagen; oxygen and strontium isotopes were measured in tooth enamel. Results suggest that the majority of individuals were born on the island, if not the estate itself. Seven individuals, however, yielded enamel oxygen and strontium ratios that are inconsistent with a Barbadian origin, which strongly suggests that we are dealing with first-generation captives who were brought to the island with the slave trade. This idea is also supported by the fact that their carbon and nitrogen stable isotope values differ markedly between their teeth and bones. These intra-skeletal shifts reflect major dietary changes that probably coincided with their enslavement and forced migration to Barbados. While it is impossible to determine their exact origins, the results clearly demonstrate that the slaves did not all grow up in the same part of Africa. Instead, the data seem to suggest that they originated from at least three different areas, possibly including the Gold Coast and the Senegambia.

  3. Magnetic field and magnetic isotope effects in organic photochemical reactions. A novel probe of reaction mechanisms and a method for enrichment of magnetic isotopes

    International Nuclear Information System (INIS)

    Turro, N.J.; Kraeutler, B.

    1980-01-01

    A brief qualitative description of the theory of intersystem crossing (ISC) in radical pairs is presented. It provides a simple unified theoretical basis for understanding chemically induced nuclear polarization (CIDNP), the magnetic spin isotope effect, and magnetic field effects on chemical reactions. Examples are given in which the magnetic spin isotope effect is employed to separate 13 C (a magnetic isotope) from 12 C (a nonmagnetic isotope) more efficiently than any mechanism involving a conventional mass isotope effect, and to separate selectively 17 O (a magnetic isotope) from 16 O and 18 O (nonmagnetic isotope), which is impossible via a conventional mass isotope effect. Examples are also provided for which the magnetic field effect is utilized to control the efficiency of cage reactions of radical pairs. The observation of magnetic isotope and magnetic field effects on the photolysis of dibenzyl ketone in micellar solution is not an isolated finding. Numerous other ketones (phenyl adamantyl ketone, phenyl benzyl ketone, etc.) have been found to exhibit analogous behavior. The ideas discussed may be employed in principle, to design chemical reactions that will separate magnetic isotopes from their nonmagnetic colleagues. The key features are the requirement of a singlet-triplet crossing along the reaction coordinate, the availability of a hyperfine hole at the molecular geometry corresponding to the hole, and sufficient time for the representative point to find the hole when it arrives in the region of phase space corresponding to the hole. Magnetic field and magnetic isotope effects provide a complement to CIDNP for probing mechanisms of radical reactions

  4. Molybdenum and Osmium isotope evidence for palaeoceanographic changes in the Arctic Ocean over the Paleocene-Eocene Thermal Maximum (PETM)

    Science.gov (United States)

    Dickson, A. J.; Cohen, A. S.; Coe, A. L.

    2010-12-01

    The Paleocene Eocene Thermal Maximum (PETM) was a period of substantial global warming thought to have been caused by the sudden input of large amounts of carbon to the ocean/atmosphere system. This carbon may have been sourced from the dissociation of methane hydrate reservoirs, although there is some debate over the role of other carbon sources, e.g. from thermogenic combustion of organic rich marine sediments during the emplacement of the North Atlantic Igneous Province. We present the first Molybdenum (Mo) and Osmium (Os) isotope data measured over the PETM interval of IODP 302 (Arctic Ocean) that reflect changes in ocean oxygenation (Mo), and in the balance between the weathering of old terrestrial rocks and younger basaltic material (Os). Both records display downcore variations that reflect the widely-recognised PETM carbon isotope excursion, suggesting clear changes in oxygenation state and weathering inputs over this event. Furthermore, isotope mass-balance constraints and comparison with other published datasets provides evidence that the Arctic Ocean remained connected to the global ocean over the course of the PETM. We will examine the implications of the new datasets for our understanding of climate dynamics during this interval.

  5. Ancient feeding ecology inferred from stable isotopic evidence from fossil horses in South America over the past 3 Ma

    Directory of Open Access Journals (Sweden)

    Alberdi María T

    2011-06-01

    Full Text Available Abstract Background Stable isotope ratios (13C/12C and 18O/16O in fossil teeth and bone provide key archives for understanding the ecology of extinct horses during the Plio-Pleistocene in South America; however, what happened in areas of sympatry between Equus (Amerhippus and Hippidion is less understood. Results Here, we use stable carbon and oxygen isotopes preserved in 67 fossil tooth and bone samples for seven species of horses from 25 different localities to document the magnitude of the dietary shifts of horses and ancient floral change during the Plio-Pleistocene. Dietary reconstructions inferred from stable isotopes of both genera of horses present in South America document dietary separation and environmental changes in ancient ecosystems, including C3/C4 transitions. Stable isotope data demonstrate changes in C4 grass consumption, inter-species dietary partitioning and variation in isotopic niche breadth of mixed feeders with latitudinal gradient. Conclusions The data for Hippidion indicate a preference varying from C3 plants to mixed C3-C4 plants in their diet. Equus (Amerhippus shows three different patterns of dietary partitioning Equus (A. neogeus from the province of Buenos Aires indicate a preference for C3 plants in the diet. Equus (A. andium from Ecuador and Equus (A. insulatus from Bolivia show a preference for to a diet of mixed C3-C4 plants, while Equus (A. santaeelenae from La Carolina (sea level of Ecuador and Brazil are mostly C4 feeders. These results confirm that ancient feeding ecology cannot always be inferred from dental morphology. While the carbon isotope composition of horses skeletal material decreased as latitude increased, we found evidence of boundary between a mixed C3/C4 diet signal and a pure C4 signal around 32° S and a change from a mixed diet signal to an exclusively C3 signal around 35°S. We found that the horses living at high altitudes and at low to middle latitude still have a C4 component in their

  6. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela

    2009-01-01

    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  7. Silver diffusion and isotope effect in silver rubidium iodide

    International Nuclear Information System (INIS)

    Arzigian, J.S.

    1980-01-01

    The diffusion coefficient of silver in RbAg 4 I 5 was measured in both superionic phases using radiotracer Ag-110m and serial sectioning with a low temperature sectioning apparatus. The activation energies for diffusion in alpha-RbAg 4 I 5 and beta-RbAg 4 I 5 , respectively, are 0.11 +- 0.01 eV and 0.20 +- 0.04 eV. An isotope effect for diffusion was also measured in both superionic phases. Ag-105 and Ag-110m radioisotopes were used with gamma spectroscopy and energy discrimination. The effect is small, with no significant temperature variation, with the value at 333 0 K being 0.12 +- 0.01. The second-order phase transition at 208 0 K has a small effect, if any, on the magnitude of the effect. The data suggest that a highly cooperative transport mechanism is responsible for the unusually high values of both the conductivity and diffusion coefficient. Although it is not possible to deduce the particular mechanism involved, theories inolving ionic polarons, or cooperative motion, such as crowdions or solitons, seem consistent with the observed results

  8. Carbonate clumped isotope variability in shallow water corals: Temperature dependence and growth-related vital effects

    Science.gov (United States)

    Saenger, Casey; Affek, Hagit P.; Felis, Thomas; Thiagarajan, Nivedita; Lough, Janice M.; Holcomb, Michael

    2012-12-01

    Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Δ47) is a novel paleotemperature proxy based on the temperature dependent "clumping" of 13C-18O bonds. Similar Δ47-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Δ47 vital effects. Here, we present the first systematic survey of Δ47 in shallow water corals. Sub-annual Red Sea Δ47 in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Δ47 values that consistently underestimate temperature by ˜8 °C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Δ47 vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra- and inter-coral comparisons suggest that the deviation from expected Δ47 increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will

  9. Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

    Science.gov (United States)

    Böhlke, J.K.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Abbene, I.; Mroczkowski, S.J.

    2009-01-01

    Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4--bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this hasbeenlargely circumstantial. Here we report ClO4- stable isotope data (??37Cl, ??18O, and ??17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4- contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased withgroundwaterage, possiblybecauseof decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO 3- fertilizers in recent years. Because ClO 4-/NO3- ratios of Atacama NO 3- fertilizers imported in the past (???2 ?? 10-3 mol mol-1) were much higher than the ClO 4-/NO3- ratio of recommended drinking-water limits (7 ?? 10-5 mol mol-1 in New York), ClO4- could exceed drinkingwater limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century. ?? 2009 American Chemical Society.

  10. Determination of the variation of mercury isotope concentration based on spectral-phase effects

    International Nuclear Information System (INIS)

    Ganeev, A.A.; Man', D.D.; Turkin, Yu.I.

    1988-01-01

    A method of isotopic atomic-absorption analysis, based on spectral-phase effects in which there is no need to use several sources of radiation with pure isotopes of the analyte element, was developed. The method made it possible to simplify the analysis and to determine the variation of the concentration of mercury isotopes from one deposit to another with an accuracy several times higher that of traditional methods of spectral isotopic analysis. The method was tested on mercury 198 and mercury 202. The isotopic analyzer is diagramed and described. The mechanism of spectral-phase effects was determined by the difference in effective photon lifetimes, corresponding to different components of the hyperfine structure of the resonance line of mercury at 254 nm

  11. Magnesium isotope evidence for single stage formation of CB chondrules by colliding planetesimals

    DEFF Research Database (Denmark)

    Olsen, Mia Bjørg Stolberg; Schiller, Martin; Krot, Alexander N.

    2013-01-01

    Chondrules are igneous spherical objects preserved in chondritic meteorites and believed to have formed during transient heating events in the solar protoplanetary disk. Chondrules present in the metal-rich CB chondrites show unusual chemical and petrologic features not observed in other chondrite...... groups, implying a markedly distinct formation mechanism. Here, we report high-precision Mg-isotope data for 10 skeletal olivine chondrules from the Hammadah al Hamra 237 (HH237) chondrite to probe the formation history of CB chondrules. The Al/Mg ratios of individual chondrules are positively correlated...... to their stable Mg-isotope composition (μMg), indicating that the correlated variability was imparted by a volatility-controlled process (evaporation/condensation). The mass-independent Mg composition (μMg*) of chondrules is consistent with single stage formation from an initially homogeneous magnesium reservoir...

  12. High-resolution isotopic evidence of specialised cattle herding in the European Neolithic

    Science.gov (United States)

    Doppler, Thomas; Heyd, Volker; Knipper, Corina; Kuhn, Thomas; Lehmann, Moritz F.; Pike, Alistair W. G.; Schibler, Jörg

    2017-01-01

    Reconstructing stock herding strategies and land use is key to comprehending past human social organization and economy. We present laser-ablation strontium and carbon isotope data from 25 cattle (Bos taurus) to reconstruct mobility and infer herding management at the Swiss lakeside settlement of Arbon Bleiche 3, occupied for only 15 years (3384–3370 BC). Our results reveal three distinct isotopic patterns that likely reflect different herding strategies: 1) localized cattle herding, 2) seasonal movement, and 3) herding away from the site year-round. Different strategies of herding are not uniformly represented in various areas of the settlement, which indicates specialist modes of cattle management. The pressure on local fodder capacities and the need for alternative herding regimes must have involved diverse access to grazing resources. Consequently, the increasing importance of cattle in the local landscape was likely to have contributed to the progress of socio-economic differentiation in early agricultural societies in Europe. PMID:28746367

  13. High-resolution isotopic evidence of specialised cattle herding in the European Neolithic.

    Directory of Open Access Journals (Sweden)

    Claudia Gerling

    Full Text Available Reconstructing stock herding strategies and land use is key to comprehending past human social organization and economy. We present laser-ablation strontium and carbon isotope data from 25 cattle (Bos taurus to reconstruct mobility and infer herding management at the Swiss lakeside settlement of Arbon Bleiche 3, occupied for only 15 years (3384-3370 BC. Our results reveal three distinct isotopic patterns that likely reflect different herding strategies: 1 localized cattle herding, 2 seasonal movement, and 3 herding away from the site year-round. Different strategies of herding are not uniformly represented in various areas of the settlement, which indicates specialist modes of cattle management. The pressure on local fodder capacities and the need for alternative herding regimes must have involved diverse access to grazing resources. Consequently, the increasing importance of cattle in the local landscape was likely to have contributed to the progress of socio-economic differentiation in early agricultural societies in Europe.

  14. Oxygen isotopic evidence for vigorous mixing during the Moon-forming giant impact.

    Science.gov (United States)

    Young, Edward D; Kohl, Issaku E; Warren, Paul H; Rubie, David C; Jacobson, Seth A; Morbidelli, Alessandro

    2016-01-29

    Earth and the Moon are shown here to have indistinguishable oxygen isotope ratios, with a difference in Δ'(17)O of -1 ± 5 parts per million (2 standard error). On the basis of these data and our new planet formation simulations that include a realistic model for primordial oxygen isotopic reservoirs, our results favor vigorous mixing during the giant impact and therefore a high-energy, high-angular-momentum impact. The results indicate that the late veneer impactors had an average Δ'(17)O within approximately 1 per mil of the terrestrial value, limiting possible sources for this late addition of mass to the Earth-Moon system. Copyright © 2016, American Association for the Advancement of Science.

  15. Titanium isotopic evidence for felsic crust and plate tectonics 3.5 billion years ago.

    Science.gov (United States)

    Greber, Nicolas D; Dauphas, Nicolas; Bekker, Andrey; Ptáček, Matouš P; Bindeman, Ilya N; Hofmann, Axel

    2017-09-22

    Earth exhibits a dichotomy in elevation and chemical composition between the continents and ocean floor. Reconstructing when this dichotomy arose is important for understanding when plate tectonics started and how the supply of nutrients to the oceans changed through time. We measured the titanium isotopic composition of shales to constrain the chemical composition of the continental crust exposed to weathering and found that shales of all ages have a uniform isotopic composition. This can only be explained if the emerged crust was predominantly felsic (silica-rich) since 3.5 billion years ago, requiring an early initiation of plate tectonics. We also observed a change in the abundance of biologically important nutrients phosphorus and nickel across the Archean-Proterozoic boundary, which might have helped trigger the rise in atmospheric oxygen. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  16. Isotope evidence for soil organic carbon pools with distinct turnover rates—II. Humic substances

    OpenAIRE

    Lichtfouse, Eric; Dou, Sen; Houot, Sabine; Barriuso, Enrique

    1995-01-01

    International audience; Two experiments using 13C-enriched substrates have been undertaken to evaluate the relative turnover rates of the main pools of soil organic carbon namely bulk organic carbon, humin and humic acids. Firstly, soil organic matter was labelled naturally during a 5 year field experiment by cultivating Zea mays, a C4 plant, on a soil that had previously grown isotopically distincts C3 plants, e.g. wheat. Secondly, soil organic matter was labelled artificially with either Im...

  17. Phosphate oxygen isotopic evidence for a temperate and biologically active Archaean ocean.

    Science.gov (United States)

    Blake, Ruth E; Chang, Sae Jung; Lepland, Aivo

    2010-04-15

    Oxygen and silicon isotope compositions of cherts and studies of protein evolution have been interpreted to reflect ocean temperatures of 55-85 degrees C during the early Palaeoarchaean era ( approximately 3.5 billion years ago). A recent study combining oxygen and hydrogen isotope compositions of cherts, however, makes a case for Archaean ocean temperatures being no greater than 40 degrees C (ref. 5). Ocean temperature can also be assessed using the oxygen isotope composition of phosphate. Recent studies show that (18)O:(16)O ratios of dissolved inorganic phosphate (delta(18)O(P)) reflect ambient seawater temperature as well as biological processing that dominates marine phosphorus cycling at low temperature. All forms of life require and concentrate phosphorus, and as a result of biological processing, modern marine phosphates have delta(18)O(P) values typically between 19-26 per thousand (VSMOW), highly evolved from presumed source values of approximately 6-8 per thousand that are characteristic of apatite in igneous rocks and meteorites. Here we report oxygen isotope compositions of phosphates in sediments from the 3.2-3.5-billion-year-old Barberton Greenstone Belt in South Africa. We find that delta(18)O(P) values range from 9.3 per thousand to 19.9 per thousand and include the highest values reported for Archaean rocks. The temperatures calculated from our highest delta(18)O(P) values and assuming equilibrium with sea water with delta(18)O = 0 per thousand (ref. 12) range from 26 degrees C to 35 degrees C. The higher delta(18)O(P) values are similar to those of modern marine phosphate and suggest a well-developed phosphorus cycle and evolved biologic activity on the Archaean Earth.

  18. Speleothem isotopic evidence for rapid human-induced expansion of grasslands in Madagascar at 890 CE

    Science.gov (United States)

    Burns, S. J.; Godfrey, L.; Faina, P.; McGee, D.; Hardt, B. F.; Ranivoharimanana, L.; Randrianasy, J.

    2015-12-01

    The degree to which human activity impacted the landscape, vegetation and fauna of Madagascar remains under debate. Since the early 1920's, the prevailing hypothesis has been that the savannah grasslands that now cover 70% of Madagascar were the result of deforestation, which has also been tied to the disappearance of much of the island's endemic megafauna. Other studies suggest that Madagascar's grasslands are largely natural and that megafaunal extinctions may be climatically induced, leading some authors to question the entire narrative of extensive alteration of the landscape by early human activity. We collected two stalagmites, M14-AB2 and M14-AB3, from Anjohibe Cave in northwestern Madagascar (15.55°S, 46.89°E, 100 masl). Age models were constructed using 8 U/Th age determinations from AB2 and 10 from AB3. The samples began to grow at ~500 CE and were active at the time of collection. Carbon and oxygen stable isotope ratios were measured on 266 samples from AB2 and 173 samples from AB3, yielding sub-decadal temporal resolution. A rapid, more than 10 per mil increase in stalagmite carbon stable isotope ratios documents an almost complete transformation of the landscape from one with a flora dominated by C3 plants to a C4 grassland system. This transformation, well replicated in both stalagmites, occurred at approximately 890 +/- 20 CE and was complete in 100 years. Further, relatively constant oxygen isotope ratios across the carbon isotope transition demonstrate that landscape alteration was not related to changes in climate. We hypothesize that the transformation was caused primarily by expansion of the use of fire by early inhabitants of Madagascar to promote agriculture and the growth of grass as fodder for cattle. The resulting loss of forest habitat very likely increased environmental pressures on Madagascar's megafauna and accelerated their disappearance.

  19. New isotopic evidence of lead contamination in wheat grain from atmospheric fallout.

    Science.gov (United States)

    Yang, Jun; Chen, Tongbin; Lei, Mei; Zhou, Xiaoyong; Huang, Qifei; Ma, Chuang; Gu, Runyao; Guo, Guanghui

    2015-10-01

    Crops could accumulate trace metals by soil-root transfer and foliar uptake from atmospheric fallout, and an accurate assessment of pollution sources is a prerequisite for preventing heavy metal pollution in agricultural products. In this study, we examined Pb isotope rates to trace the sources of Pb in wheat grain grown in suburbs. Results showed that, even in zones with scarcely any air pollution spots, atmospheric fallout was still a considerable source of Pb accumulation in wheat. The concentration of Pb in wheat grain has poor correlation with that in farm soil. The Pb concentration in wheat grains with dust in bran coat was significantly higher than that in wheat grains, which indicates that Pb may accumulate by foliar uptake. The Pb isotope rate has obvious differences between the soil and atmospheric fallout, and scatter ratio is significantly closer between the wheat grain and atmospheric fallout. Atmospheric fallout is a more significant source of Pb concentration in wheat grains than in soil. As far as we know, this is the first study on the main sources of lead in grain crop (wheat) samples with isotope. This study aims to improve our understanding of the translocation of foliar-absorbed metals to nonexposed parts of plants.

  20. Strontium isotope evidence for a highly mobile population on the Pamir Plateau 2500 years ago

    Science.gov (United States)

    Wang, Xueye; Tang, Zihua; Wu, Jing; Wu, Xinhua; Wu, Yiqun; Zhou, Xinying

    2016-10-01

    Archeological researches have proposed arguments for human mobility and long-distance trading over the Eurasia before the Silk Roads. Here we utilize biologically available strontium isotope analysis to assess the extent of pre-Silk Road population movements and cultural communications across the Asian interior. From an early Iron Age cemetery (ca. 2500 yr B.P.) on the eastern Pamir Plateau, mean 87Sr/86Sr ratios from 34 individuals display considerable isotopic variability, and 10 individuals are distinguished as migrants based on the local strontium isotope range of 0.710296-0.710572 defined by 12 ovicaprine bones. Comparison of the proportion (10/34) with the regional census data completed in 1909 A.D. (3% non-locals) suggests a highly migratory behavior on the plateau 2500 years ago. Furthermore, exotic mortuary objects, such as silk fabrics from eastern China and angular harp originated from the Near East, clearly demonstrate an interaction between different cultures on the plateau before the establishment of the Silk Road.

  1. Lead contamination in cocoa and cocoa products: isotopic evidence of global contamination.

    Science.gov (United States)

    Rankin, Charley W; Nriagu, Jerome O; Aggarwal, Jugdeep K; Arowolo, Toyin A; Adebayo, Kola; Flegal, A Russell

    2005-10-01

    In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was contamination of the finished products is tentatively attributed to atmospheric emissions of leaded gasoline, which is still being used in Nigeria. Because of the high capacity of cocoa bean shells to adsorb lead, contamination from leaded gasoline emissions may occur during the fermentation and sun-drying of unshelled beans at cocoa farms. This mechanism is supported by similarities in lead isotopic compositions of cocoa bean shells from the different farms (206Pb/207Pb = 1.1548-1.1581; 208Pb/207Pb = 2.4344-2.4394) with those of finished cocoa products (206Pb/207Pb = 1.1475-1.1977; 208Pb/207Pb = 2.4234-2.4673). However, the much higher lead concentrations and larger variability in lead isotopic composition of finished cocoa products, which falls within the global range of industrial lead aerosols, indicate that most contamination occurs during shipping and/or processing of the cocoa beans and the manufacture of cocoa and chocolate products.

  2. Biological isotopy. Introduction to the isotopic effects and to their applications in biology

    International Nuclear Information System (INIS)

    Tcherkez, G.

    2010-01-01

    Since their discovery in the beginning of the 20. century, the study of stable isotopes has considerably developed. This domain, which remained limited in its applications until the 1990's, has become particularly important thereafter thanks to its practical applications and in particular to its economical impacts. Many techniques used in fraud control, in drugs use control, in selection of high-yield plants etc are based on isotopic abundance measurements. This reference book gives a synthesis of our actual knowledge on the use of stable isotopes and of isotope fractionation in biology. It presents the basic notions of isotopic biochemistry and explains the origin of the isotopic effects. The application principles of these effects to metabolism, to organisms physiology, to environmental biology etc are explained and detailed using examples and exercises. The first chapters present the basic knowledge which defines, from a mathematical point-of-view, the isotopic effects of chemical reactions or of physical processes taking place in biology. The measurements principle of natural isotopes abundance is then synthesised. Finally, all these notions are applied at different scales: enzymes, physiology, metabolism, environment, ecosystems and fraud crackdown. (J.S.)

  3. Kinetic isotope effects significantly influence intracellular metabolite (13) C labeling patterns and flux determination.

    Science.gov (United States)

    Wasylenko, Thomas M; Stephanopoulos, Gregory

    2013-09-01

    Rigorous mathematical modeling of carbon-labeling experiments allows estimation of fluxes through the pathways of central carbon metabolism, yielding powerful information for basic scientific studies as well as for a wide range of applications. However, the mathematical models that have been developed for flux determination from (13) C labeling data have commonly neglected the influence of kinetic isotope effects on the distribution of (13) C label in intracellular metabolites, as these effects have often been assumed to be inconsequential. We have used measurements of the (13) C isotope effects on the pyruvate dehydrogenase enzyme from the literature to model isotopic fractionation at the pyruvate node and quantify the modeling errors expected to result from the assumption that isotope effects are negligible. We show that under some conditions kinetic isotope effects have a significant impact on the (13) C labeling patterns of intracellular metabolites, and the errors associated with neglecting isotope effects in (13) C-metabolic flux analysis models can be comparable in size to measurement errors associated with GC-MS. Thus, kinetic isotope effects must be considered in any rigorous assessment of errors in (13) C labeling data, goodness-of-fit between model and data, confidence intervals of estimated metabolic fluxes, and statistical significance of differences between estimated metabolic flux distributions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Kinetic isotope effects significantly influence intracellular metabolite 13C labeling patterns and flux determination

    Science.gov (United States)

    Wasylenko, Thomas M.; Stephanopoulos, Gregory

    2014-01-01

    Rigorous mathematical modeling of carbon-labeling experiments allows estimation of fluxes through the pathways of central carbon metabolism, yielding powerful information for basic scientific studies as well as for a wide range of applications. However, the mathematical models that have been developed for flux determination from 13C labeling data have commonly neglected the influence of kinetic isotope effects on the distribution of 13C label in intracellular metabolites, as these effects have often been assumed to be inconsequential. We have used measurements of the 13C isotope effects on the pyruvate dehydrogenase enzyme from the literature to model isotopic fractionation at the pyruvate node and quantify the modeling errors expected to result from the assumption that isotope effects are negligible. We show that under some conditions kinetic isotope effects have a significant impact on the 13C labeling patterns of intracellular metabolites, and the errors associated with neglecting isotope effects in 13C-metabolic flux analysis models can be comparable in size to measurement errors associated with GC–MS. Thus, kinetic isotope effects must be considered in any rigorous assessment of errors in 13C labeling data, goodness-of-fit between model and data, confidence intervals of estimated metabolic fluxes, and statistical significance of differences between estimated metabolic flux distributions. PMID:23828762

  5. Oxygen Isotope Evidence for the Relationship between CM and CO Chondrites: Could they Both Coexist on a Single Asteroid

    Science.gov (United States)

    Greenwood, R. C.; Howard, K. T.; Franchi, I. A.; Zolensky, M. E.; Buchanan, P. C.; Gibson, J. M.

    2014-01-01

    Water played a critical role in the early evolution of asteroids and planets, as well as being an essential ingredient for life on Earth. However, despite its importance, the source of water in the inner solar system remains controversial. Delivery of water to Earth via comets is inconsistent with their relatively elevated D/H ratios, whereas carbonaceous chondrites (CCs) have more terrestrial-like D/H ratios [1]. Of the eight groups into which the CCs are divided, only three (CI, CM, CR) show evidence of extensive aqueous alteration. Of these, the CMs form the single most important group, representing 34% of all CC falls and a similar percentage of finds (Met. Bull. Database). CM material also dominates the population of CC clasts in extraterrestrial samples [2, 3]. The Antarctic micrometeorites population is also dominated by CM and CI-like material and similar particles may have transported water and volatiles to the early Earth [4]. CCs, and CMs in particular, offer the best opportunity for investigating the evolution of water reservoirs in the early solar system. An important aspect of this problem involves identifying the anhydrous silicate component which co-accreted with ice in the CM parent body. A genetic relationship between the essentially anhydrous CO group and the CMs was proposed on the basis of oxygen isotope evidence [5]. However, previous CM whole-rock oxygen isotope data scattered about a line of approximately 0.5 that did not intersect the field of CO chondrites [5]. Here we discuss new oxygen isotope data which provides additional constraints on the relationship between CO and CM chondrites.

  6. Isotope effect of impurity diffusion of cadmium in silver

    International Nuclear Information System (INIS)

    Rockosch, H.J.; Herzig, C.

    1984-01-01

    The isotope effect of impurity diffusion of cadmium in silver single crystals was measured with the radioisotopes 115 Cd/ 109 Cd by gamma spectrometry. As a mean value E = 0.37 at T = 1060 K was obtained. The correlation factor f /SUB Cd/ = 0.41 is in disagreement with previous results of other investigators due to their unfavourable experimental approach. The present value of f /SUB Cd/ , however, is consistent with those of In and Sn in Ag. A comparison with the corresponding correlation factors in the copper solvent reveals a distinct influence of lattice perturbations because of the different atomic volumes of the solvents. Since the size effect is neglected in the electrostatic diffusion model, the agreement with this model is only qualitative. The frequency ratios for vacancy jumps were calculated. The free binding enthalpy of the vacancy-impurity complex was estimated to be Δg /SUB Cd/ = -0.064 eV. This value is smaller than those for In and Sn in Ag and complies with the relative diffusivities of these impurities in Ag

  7. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography

    Directory of Open Access Journals (Sweden)

    Ibrahim Ismail

    2013-03-01

    Full Text Available The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ε’s, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ε’s, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated.

  8. Isotope effects in lithium hydride and lithium deuteride crystals by molecular dynamics simulations.

    Science.gov (United States)

    Dammak, Hichem; Antoshchenkova, Ekaterina; Hayoun, Marc; Finocchi, Fabio

    2012-10-31

    Molecular dynamics (MD) simulations have been carried out to study isotope effects in lithium hydride and lithium deuteride crystals. Quantum effects on nuclear motion have been included through a quantum thermal bath (QTB). The interatomic forces were described either within the density functional theory (DFT) in the generalized gradient approximation (GGA) or by the phenomenological approach using the shell model. For both models, the isotopic shift in the lattice parameter can be successfully predicted by QTB-MD simulations. The slope of the experimental isotopic shift in pressure is satisfactorily reproduced by QTB-MD within DFT-GGA, in contrast to both density functional perturbation theory and QTB-MD with the shell model. We have analyzed the reasons for these discrepancies through the vibrational densities of states and the isotopic shifts in bulk modulus. The results illustrate the importance of anharmonic contributions to vibrations and to the isotopic pressure shift between LiH and LiD.

  9. Zn and C isotopic evidence of climatic change during the Marinoan

    Science.gov (United States)

    Thiemens, M. M.; Moynier, F.; Koeberl, C.; Thiemens, M. H.; Shaheen, R.; Gyollai, I.; Popp, F.; Chong, K.

    2011-12-01

    The "Snowball Earth" events of the Cryogenian period are renowned for their remarkable chemical and isotopic signatures left in the geological record. Through analysis of post Marinoan glaciation cap carbonates from Namibia, specifically from Fransfontein, the Khowarib Valley, and Naraachamspos, a multi isotopic study was undertaken. We analyzed the δ 13C of chemically isolated calcite and dolomite. A moderate depletion of 13C in calcite (δ 13C<0% V-PDB) associated with global glaciations was observed, confirming the event. Associated dolomites also show a 13C depletion, but at a much lower magnitude. Zinc is a trace element that is necessary for all forms of life. Zn does not undergo redox cycling under normal environmental conditions, and biological uptake is one of the few processes that produces isotopic fractionation. This fractionation is in the range of 0.1 permil for the 66Zn/64Zn ratio (δ 66Zn in permil deviation), however with the advent of multi-collection inductively-coupled plasma mass spectrometry (MC-ICP-MS) such variations have become resolvable. We also have measured the Zinc composition of multiple species of lab cultured archaea, and found that the cells are enriched in the light isotopes of Zn compared to the culture medium. By measuring Zn levels in the Cap Carbonates, we seek corroboration for the carbon depletion we find during the glaciation. Zinc should undergo a similarly significant alteration at the mass extinction from climatic shifts inherent to a worldwide glaciation. We find the samples to be relatively consistent, with a δ 66Zn of approximately 0.30 to 0.40 in most places, with a δ 68Zn of double that, values typical of terrestrial rocks. Several sites have a much larger fractionation, with δ 66Zn of up to 0.90 in the Khowarib Valley, and up to 1.06 in the clays at the entrance to the South Valley. These isotopic compositions may be indicative of the massive climatic event leading to the formation of the cap carbonates.

  10. Effect of interband interaction on isotope effect exponent of MgB2 ...

    Indian Academy of Sciences (India)

    Abstract. The exact formula of Tc's equation and the isotope effect exponent of two- band s-wave superconductors in the weak-coupling limit are derived by considering the influence of interband interaction. In each band, our model consists of two pairing inter- actions: the electron–phonon interaction and ...

  11. A Zonal Mode in the Indian Ocean over the Past Millennium? Isotopic Evidence from Continental Climate Archives and Model Simulations

    Science.gov (United States)

    Konecky, B.; Russell, J. M.; Vuille, M.; Rodysill, J. R.; Cohen, L. R.; Chuman, A. F.; Huang, Y.

    2011-12-01

    We present new evidence for multi-decadal to millennial scale hydro-climatic change in the continental Indian Ocean region over the past two millennia. We assess regional hydrological variability using new records of the δD of terrestrial plant waxes from the sediments of several lakes in tropical East Africa and Indonesia. We compare these new data to previous δ18O and δD records from the region and interpret these results in light of an isotope-enabled climate model simulation of the past 130 years. Long-term trends in our data support a southward migration of the Intertropical Convergence Zone (ITCZ)'s mean position over the past millennium, bringing progressively wetter conditions and D-depleted waxes to our southernmost site (~8°S) starting around 950 C.E. while maintaining overall wet conditions at our northernmost site (~0°N) until the end of the 19th century. Superimposed on this long-term trend are a series of pronounced, multi-decadal to centennial scale isotopic excursions that are of the same timing but in opposite directions on the two sides of the Indian Ocean. These zonally asymmetric isotopic fluctuations become progressively more pronounced beginning around 1400 C.E., with the onset of Little Ice Age cool conditions recorded in sea surface temperature reconstructions from the Northern Hemisphere and the Indo-Pacific Warm Pool (IPWP). Previous work in the IPWP region suggests cooler SST, reduced boreal summer Asian monsoon intensity, and less ENSO-like activity during the Little Ice Age [Oppo et al., 2009, Nature 460:1113, and references therein], although recent paleolimnological reconstructions from Java indicate punctuated droughts during this time [Rodysill et al., 2010, Eos Trans. AGU, 91(52), Fall Meet. Suppl., Abstract PP51B-04]. Our records suggest that multi-decadal to centennial precipitation variability was in fact enhanced during this time period in parts of equatorial East Africa and western Indonesia. The direction of isotopic

  12. Using isotopic evidence to assess the impact of migration and the two-layer hypothesis in prehistoric Northeast Thailand.

    Science.gov (United States)

    King, Charlotte L; Tayles, Nancy; Higham, Charles; Strand-Viđarsdóttir, Una; Bentley, R Alexander; Macpherson, Colin G; Nowell, Geoff

    2015-09-01

    The nature of the agricultural transition in Southeast Asia has been a topic of some debate for archaeologists over the past decades. A prominent model, known as the two-layer hypothesis, states that indigenous hunter-gatherers were subsumed by the expansion of exotic Neolithic farmers into the area around 2000 BC. These farmers had ultimate origins in East Asia and brought rice and millet agriculture. Ban Non Wat is one of the few archaeological sites in Southeast Asia where this model can potentially be tested. The site is located in the Mun River valley of Northeast Thailand, and divided into 12 phases that span over 2,000 years, from about 1750 BC to the end of the Iron Age (ca. 500 AD). These phases exhibit successive cultural changes, and current interpretation of the site is of an early hunter-gatherer population, with agriculturalists immigrating into the later phases. We analyzed strontium, oxygen, and carbon isotopes in tooth enamel from over 150 individuals, dating from the Neolithic to Iron Age, to assess extrinsic origins and differences in diet between early and later phases. We find evidence of dietary and cultural differences between groups at Ban Non Wat during its early occupation, but little evidence for immigration from distinct environments beyond the Khorat Plateau of Northeast Thailand. The lack of consistent isotopic differences between early and later Neolithic occupants at Ban Non Wat means that the site does not conclusively support the two-layer hypothesis. © 2015 Wiley Periodicals, Inc.

  13. Thermal Conductivity of Nanotubes: Effects of Chirality and Isotope Impurity

    OpenAIRE

    Gang, Zhang; Li, Baowen

    2005-01-01

    We study the dependence of thermal conductivity of single walled nanotubes (SWNT) on chirality and isotope impurity by nonequilibrium molecular dynamics method with accurate potentials. It is found that, contrary to electronic conductivity, the thermal conductivity is insensitive to the chirality. The isotope impurity, however, can reduce the thermal conductivity up to 60% and change the temperature dependence behavior. We also study the dependence of thermal conductivity on tube length for t...

  14. Investigation of the feeding effect on the 13C/12C isotope ratio of the hormones in bovine urine using gas chromatography/combustion isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Balizs, Gabor; Jainz, Annett; Horvatovich, Peter

    2005-01-01

    The effect of the feeding on the 13C/12C isotope ratio of four endogenous steroid hormones testosterone (T), epi-testosterone (epi-T), dehydroepiandrosterone (DHEA) and etiocholanolone (ETIO) in bovine urine was investigated. An analytical method to determine the accurate isotope ratio was developed

  15. Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Maggi, F.M.; Riley, W.J.

    2009-06-01

    The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

  16. Sr ISOTOPIC EVIDENCE FOR STUDYING THE SALINIZATION OF SOILS: AN EXAMPLE FROM THE SAN VITALE PINEWOOD (RAVENNA

    Directory of Open Access Journals (Sweden)

    Umberto Masi

    2009-12-01

    Full Text Available In the frame of a multidisciplinary project of research on the San Vitale Pinewood ecosystem, north of Ravenna, the Sr isotope study of a soil profile developed on an old coastal dune aiming at detecting the effect of salinization is presented. The Sr isotope ratios of the bulk soil samples decreased significantly from upper (0.717 to lower (0.712 horizons because of the abundant marine salts deposited by the brackish water present in the deep soil. While the main source of Sr in the upper horizons is the silicates, especially the feldspaths contained in the old dune sediments; in contrast, Sr in the lower horizons is significantly also of evaporitic origin (0.707-0.709. This latter is dominantly the strontium bio-available to the plants.

  17. Heavy Atom Secondary Kinetic Isotope Effect on H-Tunneling.

    Science.gov (United States)

    Eckhardt, André K; Gerbig, Dennis; Schreiner, Peter R

    2018-02-08

    Although frequently employed, heavy atom kinetic isotope effects (KIE) have not been reported for quantum mechanical tunneling reactions. Here we examine the secondary KIE through 13 C-substitution of the carbene atom in methylhydroxycarbene (H 3 C-C̈-OH) in its [1,2]H-tunneling shift reaction to acetaldehyde (H 3 C-CHO). Our study employs matrix-isolation IR spectroscopy in various inert gases and quantum chemical computations. Depending on the choice of the matrix host gas, the KIE varies within a range of 1.0 in xenon to 1.4 in neon. A KIE of 1.1 was computed using the Wentzel-Kramers-Brillouin (WKB) CVT/SCT, and instanton approaches for the gas phase at the B3LYP/cc-pVTZ level of theory. Computations with explicit consideration of the noble gas environment indicate that the surrounding atoms influence the tunneling reaction barrier height and width. The tunneling half-lives computed with the WKB approach are in good agreement with the experimental results in the different noble gases.

  18. Chlorine isotope evidence for the anthropogenic origin of tris-(4-chlorophenyl)methane

    International Nuclear Information System (INIS)

    Holmstrand, Henry; Zencak, Zdenek; Mandalakis, Manolis; Andersson, Per; Gustafsson, Orjan

    2010-01-01

    Research highlights: → TCPMe is a bioaccumulating organochlorine found at significant levels in organisms at high trophic levels, e.g. birds and mammals. → Previous investigations have suggested TCPMe being co-released as a trace byproduct in pesticides such as DDT. → The results from compound-specific chlorine isotope analysis of TCPMe supports the hypothesis that the source of TCPMe is indeed the extensive historical use of DDT. - Abstract: Compound-specific Cl-isotope analysis was performed on the persistent and bioaccumulating compound tris-(4-chlorophenyl)methane (4,4',4''-TCPMe, referred to as TCPMe in this study) to elucidate whether its main source is natural or anthropogenic. Blubber from the Baltic grey seal (Halichoerus grypus) was extracted by continuous acetonitrile partitioning, and the TCPMe was isolated from the extract by preparative-capillary gas chromatography. Chlorine isotope analysis was subsequently performed by sealed-tube combustion in conjunction with thermal-ionization mass spectrometry (TIMS). The δ 37 Cl of TCPMe was -3.5 ± 0.5 per mille, similar to the previously reported δ 37 Cl of technical grade p,p'-DDT (referred to as DDT in this study). The data is not consistent with a putative marine natural source of TCPMe, as enzymatic (biotic) production is reported to give values of δ 37 Cl 37 Cl-TCPMe data thus supports the hypothesis that TCPMe is produced as a byproduct during DDT synthesis and is released to the environment through the same pathways as DDT. It is also consistent with tris-(4-chlorophenyl)methanol as the primary biotransformation product of TCPMe.

  19. Tungsten isotopic evidence for disproportional late accretion to the Earth and Moon.

    Science.gov (United States)

    Touboul, Mathieu; Puchtel, Igor S; Walker, Richard J

    2015-04-23

    Characterization of the hafnium-tungsten systematics ((182)Hf decaying to (182)W and emitting two electrons with a half-life of 8.9 million years) of the lunar mantle will enable better constraints on the timescale and processes involved in the currently accepted giant-impact theory for the formation and evolution of the Moon, and for testing the late-accretion hypothesis. Uniform, terrestrial-mantle-like W isotopic compositions have been reported among crystallization products of the lunar magma ocean. These observations were interpreted to reflect formation of the Moon and crystallization of the lunar magma ocean after (182)Hf was no longer extant-that is, more than about 60 million years after the Solar System formed. Here we present W isotope data for three lunar samples that are more precise by a factor of ≥4 than those previously reported. The new data reveal that the lunar mantle has a well-resolved (182)W excess of 20.6 ± 5.1 parts per million (±2 standard deviations), relative to the modern terrestrial mantle. The offset between the mantles of the Moon and the modern Earth is best explained by assuming that the W isotopic compositions of the two bodies were identical immediately following formation of the Moon, and that they then diverged as a result of disproportional late accretion to the Earth and Moon. One implication of this model is that metal from the core of the Moon-forming impactor must have efficiently stripped the Earth's mantle of highly siderophile elements on its way to merge with the terrestrial core, requiring a substantial, but still poorly defined, level of metal-silicate equilibration.

  20. Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation.

    Science.gov (United States)

    Bao, Huiming; Lyons, J R; Zhou, Chuanming

    2008-05-22

    Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.

  1. Nutrient variations and isotopic evidences of particulate organic matter provenance in fringing reefs, South China

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Di; Cao, Wenzhi, E-mail: wzcao@xmu.edu.cn; Liang, Ying; Huang, Zheng

    2016-10-01

    Nutrient over-enrichment is considered to be one of the causes of coral decline. Increase in traditional fishing in the Xuwen National Coral Reefs Reserve tract (XW) and tourism around the Sanya National Coral Reefs Reserve tract (SY) are causing this coral decline. This study reviews the current state of knowledge of the nutrient status of coastal fringing reefs in South China and evaluates the primary sources of nutrients using stable isotope method. Surveys of seawater nutrients showed that the seawater remained clean in both the XW and SY coastal coral reef areas. Based on the isotopic differences between anthropogenic sewage and naturally occurring aquatic nutrients, the isotopic values of particulate organic matter (POM) and the C/N ratios were successfully used to identify the presence of anthropogenic nutrients in aquatic environments. The δ{sup 13}C, δ{sup 15}N and C/N compositions of POM from XW and SY (− 21.18 ± 2.11‰, 10.30 ± 5.54‰, and 5.35 ± 0.69 and − 20.80 ± 1.34‰, 7.06 ± 3.95‰, and 5.77 ± 2.15, respectively) showed statistically significant variations with the season. The δ{sup 13}C and δ{sup 15}N values of POM suggest marine and terrestrial-derived nutrient sources. Organic carbon is a mixture of marine phytoplankton, marine benthic algae and terrestrial-derived plants. The δ{sup 15}N values suggest terrestrial-derived sewage and upwelling-dominated nitrogen sources. In the presence of natural upwelling and coastal currents, coastal coral reef areas are more vulnerable to the increasing anthropogenic nutrient inputs. Anthropogenic activities might lead to large increases in the nutrient concentrations and could trigger the shift from coral- to macroalgae-dominated ecosystems, which would ultimately result in the degradation of the coastal coral reef ecosystem. These results provide some understanding of the declining coral reef ecosystem and the importance of conservation areas and coastal coral reef resource management

  2. Isotopic evidence for chondritic Lu/Hf and Sm/Nd of the Moon

    OpenAIRE

    Sprung Peter; Kleine Thorsten; Scherer Erik E.

    2013-01-01

    Refractory lithophile elements are generally considered to occur in chondritic relative abundances in terrestrial planets. This assumption forms the basis for using isotope systems such as 176Lu 176Hf and 146 147Sm 142 143Nd as tracers of planetary evolution. However on the basis of high precision 142Nd measurements higher than chondritic Sm/Nd and Lu/Hf values have been recently proposed for the Earth Moon and Mars. This hypothesis can be tested using the combined 147Sm 143Nd and 176Lu 176Hf...

  3. Isotopic and hydrochemical evidence of groundwater recharge in the Hopq Desert, NW China

    International Nuclear Information System (INIS)

    Jian Ge; Tao Wang; Yafei Chen; Jiansheng Chen; Hohai University, Nanjing, Jiangsu Province; Lu Ge; Chao Wang

    2016-01-01

    Artesian wells and lakes are found in the hinterland of the Hopq Desert, China. Analysis of soil profiles has revealed that the local vadose zone is always in a state of water deficit because of strong evaporation, and precipitation cannot infiltrate into the groundwater. This research indicated that soil water and surface water are recharged by groundwater and that the groundwater is recharged via an external source. Analyses of the stable isotopes in precipitation and of the water budget suggested that surface water in the Qiangtang Basin on the Tibetan Plateau might correspond to the groundwater in the Hopq Desert. (author)

  4. Nutrient variations and isotopic evidences of particulate organic matter provenance in fringing reefs, South China

    International Nuclear Information System (INIS)

    Cao, Di; Cao, Wenzhi; Liang, Ying; Huang, Zheng

    2016-01-01

    Nutrient over-enrichment is considered to be one of the causes of coral decline. Increase in traditional fishing in the Xuwen National Coral Reefs Reserve tract (XW) and tourism around the Sanya National Coral Reefs Reserve tract (SY) are causing this coral decline. This study reviews the current state of knowledge of the nutrient status of coastal fringing reefs in South China and evaluates the primary sources of nutrients using stable isotope method. Surveys of seawater nutrients showed that the seawater remained clean in both the XW and SY coastal coral reef areas. Based on the isotopic differences between anthropogenic sewage and naturally occurring aquatic nutrients, the isotopic values of particulate organic matter (POM) and the C/N ratios were successfully used to identify the presence of anthropogenic nutrients in aquatic environments. The δ 13 C, δ 15 N and C/N compositions of POM from XW and SY (− 21.18 ± 2.11‰, 10.30 ± 5.54‰, and 5.35 ± 0.69 and − 20.80 ± 1.34‰, 7.06 ± 3.95‰, and 5.77 ± 2.15, respectively) showed statistically significant variations with the season. The δ 13 C and δ 15 N values of POM suggest marine and terrestrial-derived nutrient sources. Organic carbon is a mixture of marine phytoplankton, marine benthic algae and terrestrial-derived plants. The δ 15 N values suggest terrestrial-derived sewage and upwelling-dominated nitrogen sources. In the presence of natural upwelling and coastal currents, coastal coral reef areas are more vulnerable to the increasing anthropogenic nutrient inputs. Anthropogenic activities might lead to large increases in the nutrient concentrations and could trigger the shift from coral- to macroalgae-dominated ecosystems, which would ultimately result in the degradation of the coastal coral reef ecosystem. These results provide some understanding of the declining coral reef ecosystem and the importance of conservation areas and coastal coral reef resource management. - Highlights: • The

  5. Studies of isotopic effects in the excited electronic states of molecular systems

    International Nuclear Information System (INIS)

    1982-01-01

    Rare gas halogen (RGH) lasers serve as convenient tools for a range of photophysical processes which exhibit isotope effects. This document summarizes progress in the production of molecular systems in their electronic excited states with the aid of RGH lasers, and the various isotopic effects one can study under these conditions. We conclude that the basic physical mechanisms involved in the isotopically sensitive characteristics of excited molecular electronic states are sufficiently selective to be useful in both the detection and separation of many atomic materials

  6. Isotopic Evidence of a Wide Spectrum of Feeding Strategies in Southern Hemisphere Humpback Whale Baleen Records.

    Directory of Open Access Journals (Sweden)

    Pascale Eisenmann

    Full Text Available Our current understanding of Southern hemisphere humpback whale (Megaptera novaeangliae ecology assumes high-fidelity feeding on Antarctic krill in Antarctic waters during summer, followed by fasting during their annual migration to and from equatorial breeding grounds. An increase in the number of reported departures from this feeding/fasting model suggests that the current model may be oversimplified or, alternatively, undergoing contemporary change. Information about the feeding and fasting cycles of the two Australian breeding populations of humpback whales were obtained through stable isotope analysis of baleen plates from stranded adult individuals. Comparison of isotope profiles showed that individuals from the West Australian breeding population strongly adhered to the classical feeding model. By contrast, East Australian population individuals demonstrated greater heterogeneity in their feeding. On a spectrum from exclusive Antarctic feeding to exclusive feeding in temperate waters, three different strategies were assigned and discussed: classical feeders, supplemental feeders, and temperate zone feeders. Diversity in the inter-annual feeding strategies of humpback whales demonstrates the feeding plasticity of the species, but could also be indicative of changing dynamics within the Antarctic sea-ice ecosystem. This study presents the first investigation of trophodynamics in Southern hemisphere humpback whales derived from baleen plates, and further provides the first estimates of baleen plate elongation rates in the species.

  7. Isotopic Evidence of a Wide Spectrum of Feeding Strategies in Southern Hemisphere Humpback Whale Baleen Records.

    Science.gov (United States)

    Eisenmann, Pascale; Fry, Brian; Holyoake, Carly; Coughran, Douglas; Nicol, Steve; Bengtson Nash, Susan

    2016-01-01

    Our current understanding of Southern hemisphere humpback whale (Megaptera novaeangliae) ecology assumes high-fidelity feeding on Antarctic krill in Antarctic waters during summer, followed by fasting during their annual migration to and from equatorial breeding grounds. An increase in the number of reported departures from this feeding/fasting model suggests that the current model may be oversimplified or, alternatively, undergoing contemporary change. Information about the feeding and fasting cycles of the two Australian breeding populations of humpback whales were obtained through stable isotope analysis of baleen plates from stranded adult individuals. Comparison of isotope profiles showed that individuals from the West Australian breeding population strongly adhered to the classical feeding model. By contrast, East Australian population individuals demonstrated greater heterogeneity in their feeding. On a spectrum from exclusive Antarctic feeding to exclusive feeding in temperate waters, three different strategies were assigned and discussed: classical feeders, supplemental feeders, and temperate zone feeders. Diversity in the inter-annual feeding strategies of humpback whales demonstrates the feeding plasticity of the species, but could also be indicative of changing dynamics within the Antarctic sea-ice ecosystem. This study presents the first investigation of trophodynamics in Southern hemisphere humpback whales derived from baleen plates, and further provides the first estimates of baleen plate elongation rates in the species.

  8. Lead Isotope Characteristics of the Mindyak Gold Deposit, Southern Urals: Evidence for the Source of Metals

    Science.gov (United States)

    Chugaev, A. V.; Znamensky, S. E.

    2018-01-01

    The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide-carbonate-quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite 206Pb/204Pb = 18.250-18.336, 207Pb/204Pb = 15.645-15.653, 208Pb/204Pb = 38.179-38.461; while for late pyrite 206Pb/204Pb = 18.102-18.378, 207Pb/204Pb = 15.635-15.646, 208Pb/204Pb = 38.149-38.320. The model parameters μ2 (238U/204Pb = 9.91 ± 2), ω2 (232Th/204Pb = 38.5 ± 4), and 232Th/238U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.

  9. The crust role at Paramillos Altos intrusive belt: Sr and Pb isotope evidence

    International Nuclear Information System (INIS)

    Ostera, H.A.; Linares, E; Haller, M.J; Cagnoni, M.C

    2001-01-01

    Paramillos Altos Intrusive Belt (PAIB) (Ostera, 1996) is located in the thick skinned folded-thrust belt of Malargue, southwestern Mendoza, Argentina. Geochemical, geochronologic and isotopic studies were carried out in it (Ostera 1996, 1997, Ostera et al. 1999; Ostera et al. 2000) and these previous papers suggested a minor involvement of the crust in the genesis of the PAIB. According with Ostera et al. (2000) it is composed by stocks, laccoliths, dykes and sills which range in composition from diorites to granodiorites, and from andesites to rhyolites, and divided in five Members, which range in age from Middle Miocene to Early Miocene: a- Calle del Yeso Dyke Complex (CYDC), with sills and dykes of andesitic composition (age: 20±2 Ma). b- Puchenque-Atravesadas Intrusive Complex (PAIC), composed by dykes and stocks ranging from diorites to granodiorites (age: 12.5±1 Ma). c- Arroyo Serrucho Stock (SAS), an epizonal and zoned stock, with four facies, with K/Ar and Ar/Ar dates of 10±1 and 9.5±0.5 Ma. d- Portezuelo de los Cerros Bayos (PCB), that includes porphyritic rocks of rhyolitic composition, of 7.5±0.5 Ma. e- Cerro Bayo Vitrophyres (CBV), with andesitic sills and dykes (age: 4.8±0.2 Ma). We present in this paper new Sr and Pb isotopes data that constrain the evolution of the PAIB (au)

  10. Carbon and oxygen isotope composition of carbonates from an L6 chondrite: Evidence for terrestrial weathering from the Holbrook meteorite

    Science.gov (United States)

    Socki, R. A.; Gibson, E. K.; Jull, A. J. T.; Karlsson, H. R.

    1991-01-01

    Terrestrial weathering in meteorites is an important process which alters pristine elemental and isotopic abundances. The Holbrook L6 chondrite fell in 1912. Material was recovered at the time of the fall, in 1931, and 1968. The weathering processes operating on the freshly fallen meteorite in a semi-arid region of northeastern Arizona have been studied after a ground residence of 19 and 56 years. It has been shown that a large portion of the carbonate material in 7 Antarctic ordinary chondrites either underwent extensive isotopic exchange with atmospheric CO2, or formed recently in the Antarctic environment. In fact it has been demonstrated that hydrated Mg-carbonates, nesquehonite and hydromagnesite, formed in less than 40 years on LEW 85320. In order to help further constrain the effects of terrestrial weathering in meteorites, the carbon and oxygen isotopes extracted from carbonates of three different samples of Holbrook L6: a fresh sample at the time of the fall in 1912, a specimen collected in 1931, and a third specimen collected at the same site in 1968.

  11. Oxygen isotope evidence for past and present hydrothermal regimes of Long Valley caldera, California

    Science.gov (United States)

    Smith, Brian M.; Suemnicht, Gene A.

    1991-12-01

    Whole-rock oxygen isotope compositions of cores and cuttings from Long Valley exploration wells show that the Bishop Tuff has been an important reservoir for both fossil and active geothermal systems within the caldera. The deep Clay Pit-1 and Mammoth-1 wells on the resurgent dome penetrate mildly to strongly altered Bishop Tuff with δ 18O WR values as low as -2.6% (vs V-SMOW). The IDFU 44-16 well intercepts a thinner Bishop Tuff section with δ 18O WR values of +0.4 to +2.3%. in the western caldera moat, where milder and more sporadic 18O depletions occur in Tertiary volcanic rocks of the western caldera floor ( δ 18O WR = +2.2 to +6.4‰ ). Bishop Tuff samples from deeper parts of the 715 m RDO-8 (Shady Rest) well in the SW moat are also strongly depleted in 18O ( δ 18O WR = -1.5 to +0.6‰ ). Four shallow thermal gradient wells (469-715 m TD drilled in the western moat did not penetrate Bishop Tuff, but Early Rhyolites from two of these holes are depleted in 18O ( δ 18O WR = -1.2 to +6.0‰ inplv-1 +4.6 to +5.3%. inmlgrap-1 ), compared to lithologic equivalents from the other two holes ( δ 18O WR = +6.3 to +8.0‰ inplv-2 andmlgrap-2 ). Whole-rock oxygen isotope profiles for the resurgent dome wells are unlike profiles calculated assuming alkali feldspar-H 2O fractionation behavior and total O-isotopic equilibration with -14.3‰ fluids at measured temperatures. The sense of this divergence implies an earlier hydrothermal episode within the central caldera driven by one or more shallow intrusions. Geochemical similarities between an intrusive granophyre at the bottom of the Clay Pit-1 well and a nearby Moat Rhyolite dome with a K/Ar cooling age of ˜0.5 Ma suggest that vigorous hydrothermal activity beneath the central resurgent dome may have occurred as much as ˜0.5 m.y. ago. Calculated and measured O-isotope profiles are similar for deep wells that penetrate the western moat of the caldera, where steep temperature gradients and low δ18OWR values in

  12. Heavy-atom isotope effects on binding of reactants to lactate dehydrogenase and pyruvate kinase

    International Nuclear Information System (INIS)

    Gawlita, E.

    1993-04-01

    18 O and 13 C kinetic isotope effects have been measured on the reaction of pyruvate kinase with phospho-enol-pyruvate and ADP using a remote label technique. The magnitude of both investigated isotope effects showed a dependence on the concentration of ADP. However, while the carbon effect was simply 'washed out' to unity at high ATP concentration, the oxygen effect becomes inverse and reached 0.9928 at the highest used concentration of ADP. Such a result testifies that the assumption of the negligible effect of isotopic substitution on enzyme-substrate associations remains correct only for carbon effects. An equilibrium 18 O isotope effect on association of oxalate with lactate dehydrogenase in the presence of NADHP has been evaluated by both experimental and theoretical means. Experimental methods, which involved equilibrium dialysis and gas chromatographic/mass spectrometric measurement of isotopic ration, yielded an inverse value of 0.9840. Semiempirical methods involved vibrational analysis of oxalate in two different environments. The comparison of calculated values with the experimentally determined isotope effect indicated that the AM 1 Hamiltonian proved superior to its PM 3 counterpart in this modelling. 160 refs, 8 figs, 18 tabs

  13. Isotope effects associated with the anaerobic oxidation of sulfide by the purple photosynthetic bacterium, Chromatium vinosum

    International Nuclear Information System (INIS)

    Fry, B.; Gest, H.; Hayes, J.M.

    1984-01-01

    Small inverse isotope effects of 1-3 per thousand were consistently observed for the oxidation of sulfide to elemental sulfur during anaerobic photometabolism by Chromatium vinosum. The inverse fractionation can be accounted for by an equilibrium isotope effect between H 2 S and HS - , and may indicate that C. vinosum (and other photosynthetic bacteria) utilizes H 2 S rather than HS - as the substrate during sulfide oxidation. (Auth.)

  14. Use of intermediate partitioning to calculate intrinsic isotope effects for the reaction catalyzed by malic enzyme

    International Nuclear Information System (INIS)

    Grissom, C.B.; Cleland, W.W.

    1985-01-01

    For those enzymes that proceed via a stepwise reaction mechanism with a discrete chemical intermediate and where deuterium and 13 C isotope effects are on separate steps, a new method has been developed to solve for the intrinsic deuterium and 13 C kinetic isotope effects that relies on directly observing the partitioning of the intermediate between the forward and reverse directions. This observed partitioning ratio, along with the values of the primary deuterium, tritium, and 13 C kinetic isotope effects on V/K for the substrate with the label being followed, allows an exact solution for the intrinsic deuterium and 13 C isotope effects, the forward commitment for the deuterium-sensitive step, and the partition ratio for the intermediate in the reaction. This method allows portions of the reaction coordinate diagram to be defined precisely and the relative energy levels of certain activation barriers to be assigned exactly. With chicken liver triphosphopyridine nucleotide (TPN) malic enzyme activated by Mg 2+ , the partitioning of oxalacetate to pyruvate vs. malate in the presence of TPNH, 0.47, plus previously determined isotope effects gives an intrinsic deuterium isotope effect of 5.7 on hydride transfer and a 13 C isotope effect of 1.044 on decarboxylation. Reverse hydride transfer is 10 times faster than decarboxylation, and the forward commitment for hydride transfer is 3.3. The 13 C isotope effect is not significantly different with reduced acetylpyridine adenine dinucleotide phosphate replacing TPNH (although the pyruvate/malate partitioning ratio for oxalactate is now 9.9), but replacement of Mg 2+ by Mn 2+ raises the value to 1.065 (partition ratio 0.99)

  15. Nutrient variations and isotopic evidences of particulate organic matter provenance in fringing reefs, South China.

    Science.gov (United States)

    Cao, Di; Cao, Wenzhi; Liang, Ying; Huang, Zheng

    2016-10-01

    Nutrient over-enrichment is considered to be one of the causes of coral decline. Increase in traditional fishing in the Xuwen National Coral Reefs Reserve tract (XW) and tourism around the Sanya National Coral Reefs Reserve tract (SY) are causing this coral decline. This study reviews the current state of knowledge of the nutrient status of coastal fringing reefs in South China and evaluates the primary sources of nutrients using stable isotope method. Surveys of seawater nutrients showed that the seawater remained clean in both the XW and SY coastal coral reef areas. Based on the isotopic differences between anthropogenic sewage and naturally occurring aquatic nutrients, the isotopic values of particulate organic matter (POM) and the C/N ratios were successfully used to identify the presence of anthropogenic nutrients in aquatic environments. The δ(13)C, δ(15)N and C/N compositions of POM from XW and SY (-21.18±2.11‰, 10.30±5.54‰, and 5.35±0.69 and -20.80±1.34‰, 7.06±3.95‰, and 5.77±2.15, respectively) showed statistically significant variations with the season. The δ(13)C and δ(15)N values of POM suggest marine and terrestrial-derived nutrient sources. Organic carbon is a mixture of marine phytoplankton, marine benthic algae and terrestrial-derived plants. The δ(15)N values suggest terrestrial-derived sewage and upwelling-dominated nitrogen sources. In the presence of natural upwelling and coastal currents, coastal coral reef areas are more vulnerable to the increasing anthropogenic nutrient inputs. Anthropogenic activities might lead to large increases in the nutrient concentrations and could trigger the shift from coral- to macroalgae-dominated ecosystems, which would ultimately result in the degradation of the coastal coral reef ecosystem. These results provide some understanding of the declining coral reef ecosystem and the importance of conservation areas and coastal coral reef resource management. Copyright © 2016 Elsevier B.V. All

  16. Dietary shift after 3600 cal yr BP and its influencing factors in northwestern China: Evidence from stable isotopes

    Science.gov (United States)

    Ma, Minmin; Dong, Guanghui; Jia, Xin; Wang, Hui; Cui, Yifu; Chen, Fahu

    2017-04-01

    :Human diets rely on natural resource availability and can reflect social and cultural values. When environments, societies, and cultures change, diets may also shift. This study traced the extent of dietary change and the factors influencing such change. Through stable carbon and nitrogen isotopic analysis of late Neolithic and early Bronze Age human and animal bone collagen, we found that significant shifts in human diets were closely associated with intercontinental cultural exchanges in Eurasia and climate change in northwestern China. The isotopic evidence indicated that human diets mainly consisted of C4 foodstuffs (presumably millet and/or animals fed with C4 foods) around 4000 calibrated years before the present (cal yr BP), corresponding to the flourishing of millet agriculture in the context of the optimal climate conditions of the mid-Holocene. Subsequently, more C3 foods (probably wheat, barley, and animals fed with C3 foods) were added to human diets post-3600 cal yr BP when the climate became cooler and drier. Such dietary variation is also consistent with the increasing intensity of long-distance exchange after 4000 cal yr BP. While many factors can lead to human dietary shifts (e.g. climate change, population growth, cultural factors, and human migration), climate may have been a key factor in Gansu and Qinghai.

  17. LINES OF EVIDENCE FOR NA FOR ORGANIC COMPOUNDS AND THE USE OF COMPOUND SPECIFIC ISOTOPE ANALYSIS

    Science.gov (United States)

    The strongest line of evidence is a reduction in concentration over time. However, this only provides evidence of natural attenuation of the source area. It is difficult to determine the rate of natural attenuation through biodegradation with distance along a flow path in the a...

  18. A revisit to vityaz transform fault area, Central Indian Ridge: Isotopic evidence of probable hydrothermal activity.

    Digital Repository Service at National Institute of Oceanography (India)

    Shirodkar, P.V.; Banerjee, R.; Xiao, Y.K.

    at the Institute of Salt Lakes, China by +ve thermal ionisation mass spectrometry of Cs2BO4+ and Cs2Cl+ ions respectively, using a VG 354 model TIMS [14]. The measured isotopic ratios were expressed as del values relative to their standard reference materials.... 37.5 38 38.5 39 39.5 40 Del 11B 2000 1600 1200 800 400 0 W at er d ep th (m ) -0.2 0 0.2 0.4 0.6 0.8 Del 37Cl 2000 1600 1200 800 400 0 Figure 2: Vertical profiles of δ11B and δ37Cl in water column at Stn.VM3 in the CIR. Stn. No. Latitude Longitude...

  19. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

    DEFF Research Database (Denmark)

    van Kooten, Elishevah M. M. E.; Wielandt, Daniel Kim Peel; Schiller, Martin

    2016-01-01

    )Mg*-depleted and (54)Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived (26)Al. The (26)Mg* and (54)Cr compositions of bulk metal-rich chondrites require significant amounts (25...... addition of stellar-derived (26)Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a (26......-50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals...

  20. Tightly bound soil water introduces isotopic memory effects on mobile and extractable soil water pools.

    Science.gov (United States)

    Newberry, Sarah L; Prechsl, Ulrich E; Pace, Matthew; Kahmen, Ansgar

    2017-08-01

    Cryogenic vacuum extraction is the well-established method of extracting water from soil for isotopic analyses of waters moving through the soil-plant-atmosphere continuum. We investigate if soils can alter the isotopic composition of water through isotope memory effects, and determined which mechanisms are responsible for it. Soils with differing physicochemical properties were re-wetted with reference water and subsequently extracted by cryogenic water distillation. Results suggest some reference waters bind tightly to the soil and not all of this tightly bound water is removed during cryogenic vacuum extraction. Kinetic isotopic fractionation occurring when reference water binds to the soil is likely responsible for the 18 O-depletion of re-extracted reference water, suggesting an enrichment of the tightly bound soil water pool. Further re-wetting of cryogenically extracted soils indicates an isotopic memory effect of tightly bound soil water on water added to the soil. The data suggest tightly bound soil water can influence the isotopic composition of mobile soil water. Findings show that soils influence the isotope composition of soil water by (i) kinetic fractionation when water is bound to the soil and (ii) equilibrium fractionation between different soil water pools. These findings could be relevant for plant water uptake investigations and complicate ecohydrological and paleohydrological studies.

  1. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  2. Calcium Isotopic Evidence for Vulnerable Marine Ecosystem Structure Prior to the K/Pg Extinction.

    Science.gov (United States)

    Martin, Jeremy E; Vincent, Peggy; Tacail, Théo; Khaldoune, Fatima; Jourani, Essaid; Bardet, Nathalie; Balter, Vincent

    2017-06-05

    The collapse of marine ecosystems during the end-Cretaceous mass extinction involved the base of the food chain [1] up to ubiquitous vertebrate apex predators [2-5]. Large marine reptiles became suddenly extinct at the Cretaceous-Paleogene (K/Pg) boundary, whereas other contemporaneous groups such as bothremydid turtles or dyrosaurid crocodylomorphs, although affected at the familial, genus, or species level, survived into post-crisis environments of the Paleocene [5-9] and could have found refuge in freshwater habitats [10-12]. A recent hypothesis proposes that the extinction of plesiosaurians and mosasaurids could have been caused by an important drop in sea level [13]. Mosasaurids are unusually diverse and locally abundant in the Maastrichtian phosphatic deposits of Morocco, and with large sharks and one species of elasmosaurid plesiosaurian recognized so far, contribute to an overabundance of apex predators [3, 7, 14, 15]. For this reason, high local diversity of marine reptiles exhibiting different body masses and a wealth of tooth morphologies hints at complex trophic interactions within this latest Cretaceous marine ecosystem. Using calcium isotopes, we investigated the trophic structure of this extinct assemblage. Our results are consistent with a calcium isotope pattern observed in modern marine ecosystems and show that plesiosaurians and mosasaurids indiscriminately fall in the tertiary piscivore group. This suggests that marine reptile apex predators relied onto a single dietary calcium source, compatible with the vulnerable wasp-waist food webs of the modern world [16]. This inferred peculiar ecosystem structure may help explain plesiosaurian and mosasaurid extinction following the end-Cretaceous biological crisis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. A silicon depleted North Atlantic since the Palaeogene: Evidence from sponge and radiolarian silicon isotopes

    Science.gov (United States)

    Fontorbe, Guillaume; Frings, Patrick J.; De La Rocha, Christina L.; Hendry, Katharine R.; Conley, Daniel J.

    2016-11-01

    Despite being one of Earth's major geochemical cycles, the evolution of the silicon cycle has received little attention and changes in oceanic dissolved silica (DSi) concentration through geologic time remain poorly constrained. Silicon isotope ratios (expressed as δ30Si) in marine microfossils are becoming increasingly recognised for their ability to provide insight into silicon cycling. In particular, the δ30Si of siliceous sponge spicules has been demonstrated to be a useful proxy for past DSi concentrations. We analysed δ30Si in radiolarian tests and sponge spicules from the Blake Nose Palaeoceanographic Transect (ODP Leg 171B) spanning the Palaeocene-Eocene (ca. 60-30 Ma). Our δ30Si results range from +0.32 to + 1.67 ‰ and -0.48 to + 0.63 ‰ for the radiolarian and sponge records, respectively. Using an established relationship between ambient dissolved Si (DSi) concentrations and the magnitude of silicon isotope fractionation in siliceous sponges, we demonstrate that the Western North Atlantic was DSi deplete during the Palaeocene-Eocene throughout the water column, a conclusion that is robust to a range of assumptions and uncertainties. These data can constitute constraints on reconstructions of past-ocean circulation. Previous work has suggested ocean DSi concentrations were higher than modern ocean concentrations prior to the Cenozoic and has posited a drawdown during the Early Palaeogene due to the evolutionary expansion of diatoms. Our results challenge such an interpretation. We suggest here that if such a global decrease in oceanic DSi concentrations occurred, it must predate 60 Ma.

  4. Holocene Climate Change in Sub-Alpine Southwestern Alberta: Evidence from Oxygen and Carbon Isotope values of Hogarth Lake Marl.

    Science.gov (United States)

    Matkowski, D.; Patterson, W. P.; Timsic, S.

    2017-12-01

    A 3.6-meter lake sediment core was recovered from Upper Hogarth Lake, providing proxy evidence for climate variability over the last 11,500 years. The core was sampled at millimeter scale for high-resolution oxygen and carbon isotope values. Large variations (up to 6‰) in the carbon isotope values are attributed to the increasingly dominant role of terrestrial-sourced organic matter over bedrock-sourced DIC during initial lake formation and subsequent changes in regional humidity. Variations (up to 4‰) in oxygen isotope values of the marl are interpreted as representing changes in meteoric water source and regional temperature. The hydrologically-open, fresh-water lake is hosted in Devonian-Carboniferous carbonates, recharged via groundwater, surface flow and precipitation. Marl sediment is generated by the green algae Chara sp., with marl deposition beginning approximately 11,500 cal yBP. Our age model was constructed using tephrochronology and radiocarbon dating of 8 terrestrial plant samples, then calibrated using the University of Minnesota's "Bacon" software. The presence of an ash layer in the core was associated with the Mazama ash layer dated 7,627 ±150 yBP, and was used to support the 14C age model. Sediment deposition is characterized by 3 stages: from the recent, dating back to 11,500 cal yBP, the core is marl dominated, comprising 70% of the 3.6m core. Prior to marl deposition there is a 500-year depositional period of carbonate and allochthonous clastic material. Below 2.65 meters, the sediment consists of fine sand and mud; sourced from the weathering of surrounding bedrock. Isotope data are characterized by 5 distinct periods. 7,800 cal yBP to the end Younger Dryas ( 11,500 cal yBP) exhibits irregular, and generally decreasing, δ13C and δ18O values, with a positive excursion in δ18O values occurring around 9,000 cal yBP. Climate was stable, cool and dry from 5,000-7,000 cal yBP, evidenced by relatively invariant δ13C and δ18O values. The

  5. Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

    Energy Technology Data Exchange (ETDEWEB)

    Bohlke, J. K. [U.S. Geological Survey, Reston, VA; Hatzinger, Paul B. [Shaw Environmental, Inc., Lawrenceville, NJ; Sturchio, N. C. [University of Illinois, Chicago; Gu, Baohua [ORNL; Abbene, I. [U.S. Geological Survey; Mroczkowki, S. J. [U.S. Geological Survey

    2009-01-01

    Perchlorate (ClO{sub 4}{sup -}) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO{sub 4}{sup -} is past agricultural application of ClO{sub 4}{sup -}-bearing natural NO{sub 3}{sup -} fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO{sub 4}{sup -} stable isotope data ({delta}{sup 37}Cl, {delta}{sup 18}O, and {Delta}{sup 17}O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO{sub 4}{sup -} contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO{sub 4}{sup -} apparently was not affected by biodegradation within the aquifers. Synthetic ClO{sub 4}{sup -} was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO{sub 4}{sup -} was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO{sub 4}{sup -} concentrations and ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO{sub 3}{sup -} fertilizers and/or decreasing ClO{sub 4}{sup -} concentrations in Atacama NO{sub 3}{sup -} fertilizers in recent years. Because ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios of Atacama NO{sub 3}{sup -} fertilizers imported in the past (2 x 10{sup -3} mol mol{sup -1}) were much higher than the ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratio of recommended drinking-water limits (7 x 10{sup -5} mol mol{sup -1} in New York), ClO{sub 4}{sup -} could exceed drinking-water limits even where NO{sub 3}{sup -} does not, and where Atacama NO{sub 3}{sup -} was only a minor source of N. Groundwater ClO{sub 4}{sup -} with distinctive isotopic composition was a sensitive indicator of past Atacama NO{sub 3}{sup -} fertilizer use on Long Island and may be common in

  6. Ab Initio Calculation of the Zn Isotope Effect in Phosphates, Citrates, and Malates and Applications to Plants and Soil

    OpenAIRE

    Fujii, Toshiyuki; Albar?de, Francis

    2012-01-01

    International audience; Stable Zn isotopes are fractionated in roots and leaves of plants. Analyses demonstrate that the heavy Zn isotopes are enriched in the root system of plants with respect to shoots and leaves as well as the host soil, but the fractionation mechanisms remain unclear. Here we show that the origin of this isotope fractionation is due to a chemical isotope effect upon complexation by Zn malates and citrates in the aerial parts and by phosphates in the roots. We calculated t...

  7. Radioactive isotope and isomer separation with using light induced drift effect

    International Nuclear Information System (INIS)

    Hradecny, C.; Slovak, J.; Tethal, T.; Ermolaev, I.M.; Shalagin, A.M.

    1991-01-01

    The isotope separation with using light induced drift (LID) is discussed. The basic theoretical characteristics of the method are deduced: separation simultaneously with an arbitrary high enrichment and without significant losses; separation productivity up to 100 μg/h. These characteristics are sufficient and very convenient for separation of expensive radioactive isotopes and isomers which are applied in medicine and science. The first experimental separation of the radioactive isotopes ( 22,24 Na) by using the LID effect is reported. 13 refs.; 5 figs

  8. Evidence for the formation of dynamically created pre-formed ions at the interface of isotopically enriched thin films.

    Science.gov (United States)

    Lerach, Jordan O; Winograd, Nicholas

    2013-01-01

    A novel approach to elucidate the ionization mechanism for the [M + H] + molecular ion of organic molecules is investigated by molecular depth profiling of isotopically enriched thin films. Using a model bi-layer film of phenylalanine (PHE) and PHE-D 8 , the results show formation of an [M + D] + molecular ion for the non-enriched PHE molecule attributed to rearrangements of chemical damage due to successive primary ion impacts. The [M + D] + ion is observed at the interface for 19.9nm in the enriched-on-top system and 9.9nm for the enriched-on-bottom system. This ion formation is direct evidence for dynamically created pre-formed ions as a result of chemical damage rearrangement induced by previous primary ion bombardment events.

  9. Stable isotope evidence of ontogenetic changes in the diet of gizzard shad Dorosoma cepedianum

    DEFF Research Database (Denmark)

    De Brabandere, Loreto; Catalano, M.J.; Frazer, T.K.

    2009-01-01

    composition of the adult fish suggested an increasing importance of zooplankton in the diet, although benthic food sources remained part of the diet of all D. cepedianum collected in this study. The results indicated that benthic feeding is used by D. cepedianum of all sizes, suggesting that biomanipulation......Stable sulphur isotopic composition (d34S) of gizzard shad Dorosoma cepedianum was used to investigate the seasonal and ontogenetic variation in the diet of young and adult fish. This study evaluated fish from a hypereutrophic lake that had recently undergone a 40% reduction of large (>300 mm total...... length, LT) D. cepedianum biomass as part of a biomanipulation experiment, which aimed at reducing internal nutrient loading. Dorosoma cepedianum d34S values showed evidence of ontogenetic changes with young fish (200 mm LT). The d34S...

  10. The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

    Science.gov (United States)

    Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor

    2013-12-01

    Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that

  11. Nitrogen isotopes in the recent solar wind from the analysis of genesis targets: evidence for large scale isotope heterogeneity in the nascent solar system

    Energy Technology Data Exchange (ETDEWEB)

    Wiens, Roger C [Los Alamos National Laboratory; Marty, Bernard [INSU-CNRS; Zimmermann, Laurent [INSU-CNRS; Burnard, Peter G [INSU-CNRS; Burnett, Donald L [CALTECH; Heber, Veronika S [ETH ZURICH; Wieler, Rainer [ETH ZURICH; Bochsler, Peter [UNIV OV BERN

    2009-01-01

    Nitrogen, the fifth most abundant element in the universe, displays the largest stable isotope variations in the solar system reservoirs after hydrogen. Yet the value of isotopic composition of solar nitrogen, presumably the best proxy of the protosolar nebula composition, is not known. Nitrogen isotopes trapped in Genesis spacecraft target material indicate a 40 % depletion of {sup 15}N in solar wind N relative to inner planets and meteorites, and define a composition for the present-day Sun undistinguishable from that of Jupiter's atmosphere. These results indicate that the isotopic composition of of nitrogen in the outer convective zone of the Sun (OCZ) has not changed through time, and is representative of the protosolar nebula. Large {sup 15}N enrichments during e.g., irradiation, or contributions from {sup 15}N-rich presolar components, are required to account for planetary values.

  12. Stable isotope studies

    International Nuclear Information System (INIS)

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs

  13. Isotope effect on band gap and radiative transitions properties of boron nitride nanotubes.

    Science.gov (United States)

    Han, Wei-Qiang; Yu, Hua-Gen; Zhi, Chunyi; Wang, Jianbin; Liu, Zhenxian; Sekiguchi, Takashi; Bando, Yoshio

    2008-02-01

    We have carried out an isotope study on the band gap and radiative transition spectra of boron nitride nanotubes (BNNTs) using both experimental and theoretical approaches. The direct band gap of BNNTs was determined at 5.38 eV, independent of the nanotube size and isotope substitution, by cathodoluminescences (CL) spectra. At lower energies, several radiative transitions were observed, and an isotope effect was revealed. In particular, we confirmed that the rich CL spectra between 3.0 and 4.2 eV reflect a phonon-electron coupling mechanism, which is characterized by a radiative transition at 4.09 eV. The frequency red shift and peak broadening due to isotopic effect have been observed. Our Fourier transform infrared spectra and density functional theory calculations suggest that those radiative transitions in BNNTs could be generated by a replacement of some nitrogen atoms with oxygen.

  14. 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 manifested by a reduction in anodic current densities when H(2) was replaced by D(2). For both nickel and silver, the anodic part of the polarisation curves displayed limiting current behaviour, due to concentration polarisation. The empirical reaction order was not influenced by isotope replacement....... The empirical activation energy of the limiting current was affected by both the isotope used and the nature of the electrode. For both metals, a higher activation energy was observed with deuterium than with hydrogen. (C) 1999 Elsevier Science B.V. All rights reserved....

  15. Isotopic evidence for the source and fate of phosphorus in Everglades wetland ecosystems

    Energy Technology Data Exchange (ETDEWEB)

    Li Xin [Institute of Hydrobiology, Jinan University, Guangzhou, Guangdong 510632 (China)] [Department of Earth, Ocean and Atmospheric Science, Florida State University and National High Magnetic Field Laboratory, Tallahassee, FL 32306-4100 (United States); Wang Yang, E-mail: ywang@magnet.fsu.edu [Department of Earth, Ocean and Atmospheric Science, Florida State University and National High Magnetic Field Laboratory, Tallahassee, FL 32306-4100 (United States); Stern, Jennifer [Department of Earth, Ocean and Atmospheric Science, Florida State University and National High Magnetic Field Laboratory, Tallahassee, FL 32306-4100 (United States)] [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Gu Binhe [Everglades Division, South Florida Water Management District, West Palm Beach, FL 33406 (United States)

    2011-05-15

    Research Highlights: > Oxygen isotopic analysis of phosphate is a useful tool for studying source and degree of microbial cycling of phosphorus (P) in freshwater ecosystems. > P was quickly cycled in the water column and the dissolved inorganic phosphate (DIP) pool consisted entirely of biologically cycled P in relatively pristine areas of the Everglades wetland ecosystem. >In wetland areas highly impacted by agricultural runoff, biological cycling of P was not rapid enough to completely remove the fertilizer {delta}{sup 18}O signature. >DIP pool in these areas consisted of biologically cycled P as well as fertilizer P, with fertilizer P accounting for about 15-100% of the total DIP. - Abstract: Phosphorus has historically been a limiting nutrient in the Florida Everglades. Increased P loading to the Everglades over the past several decades has led to significant changes in water quality and plant communities. Stormwater runoff that drains agricultural lands and enters the Water Conservation Areas (WCAs) are known to contain elevated levels of P, but the exact source of this P has not been fully determined. Here the results of an O isotope study of dissolved inorganic phosphate (DIP) in both polluted and relatively pristine (or reference) areas of the Everglades are reported. The data reveal spatial and temporal variations in the {delta}{sup 18}O signature of DIP, reflecting the source and the degree of cycling of P. The {delta}{sup 18}O values of DIP collected from the Everglades National Park were close or equal to the predicted {delta}{sup 18}O values of DIP formed in situ in equilibrium with ambient water, indicating that P is quickly cycled in the water column in oligotrophic ecosystems with very low P concentrations. However, most DIP samples collected from areas impacted by agricultural runoff yielded {delta}{sup 18}O values that deviated from the predicted equilibrium DIP-{delta}{sup 18}O values based on the {delta}{sup 18}O of water and water temperature

  16. Stable isotope evidence for the Bottom Convective Layer homogeneity in the Black Sea.

    Science.gov (United States)

    Dubinin, Alexander V; Dubinina, Elena O; Demidova, Tatyana P; Kokryatskaya, Nataliya M; Rimskaya-Korsakova, Maria N; Kosova, Sofia A; Yakushev, Evgeniy V

    2014-01-01

    The Black Sea is the largest euxinic basin on the Earth. The anoxic zone consists of the upper part water mass stratified by density, and the lower water mass homogenized relative to density (depth >1750 m), named the Bottom Convective Layer. To assess homogeneity and possible exchange of matter across the upper and lower boundaries of the Bottom Convective Layer, new data on stable isotope composition of S, O and H were obtained. Samples were collected in August 2008 and March 2009 from two stations located in the eastern central part of the Black Sea. Distribution of δ(18)O and δD values of water for the entire water column did not vary seasonally. Appreciable differences were marked for δD value variation in the picnocline area (water depth 200-400 m) and in the BCL 5 m above the bottom that might be caused by penetration of intrusions with elevated portion of shelf modified Mediterranean Water. Observed linear relationship between δ(18)O (or δD) and salinity indicates that mixing water and salt occurs at the same time, and the deep water of the Black Sea has two end members: the high-salinity Mediterranean seawater and freshwater input. In the Bottom Convective Layer, the average δ(34)S (H2S) was -40.6 ± 0.5‰ and did not vary seasonally. At the bottom (depth > 2000 m), (34)S depletion down to -41.0‰ was observed. Our δ(34)S (SO4) data are by 2-3‰ higher than those measured previously for the Bottom Convective Layer. Sulfate from the aerobic zone with δ(34)S (SO4) = +21‰ corresponds to ocean water sulfate and that has not been subjected to sulfate reduction. Average δ(34)S (SO4) values for depths > 1250 m were found to be +23.0 ± 0.2‰ (1σ). Sulfur isotope composition of sulfate does not change in the Bottom Convective Layer and on its upper and lower boundaries, and does not depend on the season of observation.

  17. Isotopic Evidence for the Source and Fate of Phosphorus in Everglades Wetland Ecosystems

    Science.gov (United States)

    Li, Xin; Wang, Yang; Stern, Jennifer; Gu, Binhe

    2011-01-01

    Phosphorus has historically been a limiting nutrient in the Florida Everglades. Increased P loading to the Everglades over the past several decades has led to significant changes in water quality and plant communities. Stormwater runoff that drains agricultural lands and enters the Water Conservation Areas (WCAs) are known to contain elevated levels of P, but the exact source of this P has not been fully determined. Here the results of an O isotope study of dissolved inorganic phosphate (DIP) in both polluted and relatively pristine (or reference) areas of the Everglades are reported. The data reveal spatial and temporal variations in the delta 18O signature of DIP, reflecting the source and the degree of cycling of P. The delta 18O values of DIP collected from the Everglades National Park were close or equal to the predicted delta 18O values of DIP formed in situ in equilibrium with ambient water, indicating that P is quickly cycled in the water column in oligotrophic ecosystems with very low P concentrations. However, most DIP samples collected from areas impacted by agricultural runoff yielded delta 18O values that deviated from the predicted equilibrium DIP delta 18O values based on the delta 18O of water and water temperature, suggesting that biological cycling of P was not rapid enough to remove the fertilizer ?18O signature in the DIP pool from areas receiving high P loading. The delta 18O signature of DIP in impacted areas reflects a mixing of fertilizer P and biologically cycled P, where the relative proportions of biologically cycled vs. fertilizer DIP are controlled by both biological (microbial activities and plant uptake) and hydrologic factors (loading rate and residence time). Using a two-end-member (i.e., fertilizer P and biologically cycled P) mixing model, fertilizers were estimated to contribute about 15 100% of the DIP pool in the highly impacted areas of the northern Everglades, whereas the DIP pool in the reference (i.e., relatively pristine

  18. Isotopic evidence for anthropogenic impacts on aquatic food web dynamics and mercury cycling in a subtropical wetland ecosystem in the US

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yang, E-mail: ywang@magnet.fsu.edu [Department of Earth, Ocean and Atmospheric Science, Florida State University and National High Magnetic Field Laboratory, Tallahassee, FL 32306–4100 (United States); Gu, Binhe [South Florida Water Management District, West Palm Beach, FL 33406 (United States); Lee, Ming-Kuo [Department of Geology and Geography, Auburn University, Auburn, AL 36839 (United States); Jiang, Shijun, E-mail: sjiang@jnu.edu.cn [Institute of Hydrobiology/Laboratory of Eutrophication and Red Tide Prevention of Guangdong Higher Education Institutes, Jinan University, Guangzhou, Guangdong 510632 (China); Xu, Yingfeng [Department of Earth, Ocean and Atmospheric Science, Florida State University and National High Magnetic Field Laboratory, Tallahassee, FL 32306–4100 (United States)

    2014-07-01

    Quantifying and predicting the food web consequences of anthropogenic changes is difficult using traditional methods (based on gut content analysis) because natural food webs are variable and complex. Here, stable and radioactive carbon isotopes are used, in conjunction with nitrogen isotopes and mercury (Hg) concentration data, to document the effects of land-use change on food webs and Hg bioaccumulation in the Everglades – a subtropical wetland ecosystem in the US. Isotopic signatures of largemouth bass and sunfish in reference (relatively pristine) wetlands indicate reliance on the food supply of modern primary production within the wetland. In contrast, both fish in areas impacted by agricultural runoff had radiocarbon ages as old as 540 years B.P., and larger isotopic variability than counterparts in reference wetlands, reflecting differences in the food web between impacted and reference wetlands. Consistent with this difference, particulate and dissolved organic matter in impacted areas had old radiocarbon ages (> 600 years B.P.), indicating that old carbon derived from historic peat deposits in the Everglades Agricultural Area was passed along the food chain to consumers. Significant radiocarbon deficiencies in largemouth bass and sunfish, relative to mosquitofish, in impacted areas most likely indicate a reduced dependence on small fish. Furthermore, largemouth bass and sunfish from impacted areas had much lower Hg contents than those from reference wetlands. Taken together, these data suggest a shift toward lower trophic levels and a possible reduction in mercury methylation in impacted wetlands. Our study provides clear evidence that hydrological modification and land-use change in the Everglades have changed the system from one driven primarily by in-situ productivity to one that is partially dependent on allochthonous carbon input from peat soils in the agricultural area and altered the Hg biogeochemical cycle in the wetlands. The results have

  19. Isotopic evidence for anthropogenic impacts on aquatic food web dynamics and mercury cycling in a subtropical wetland ecosystem in the US

    International Nuclear Information System (INIS)

    Wang, Yang; Gu, Binhe; Lee, Ming-Kuo; Jiang, Shijun; Xu, Yingfeng

    2014-01-01

    Quantifying and predicting the food web consequences of anthropogenic changes is difficult using traditional methods (based on gut content analysis) because natural food webs are variable and complex. Here, stable and radioactive carbon isotopes are used, in conjunction with nitrogen isotopes and mercury (Hg) concentration data, to document the effects of land-use change on food webs and Hg bioaccumulation in the Everglades – a subtropical wetland ecosystem in the US. Isotopic signatures of largemouth bass and sunfish in reference (relatively pristine) wetlands indicate reliance on the food supply of modern primary production within the wetland. In contrast, both fish in areas impacted by agricultural runoff had radiocarbon ages as old as 540 years B.P., and larger isotopic variability than counterparts in reference wetlands, reflecting differences in the food web between impacted and reference wetlands. Consistent with this difference, particulate and dissolved organic matter in impacted areas had old radiocarbon ages (> 600 years B.P.), indicating that old carbon derived from historic peat deposits in the Everglades Agricultural Area was passed along the food chain to consumers. Significant radiocarbon deficiencies in largemouth bass and sunfish, relative to mosquitofish, in impacted areas most likely indicate a reduced dependence on small fish. Furthermore, largemouth bass and sunfish from impacted areas had much lower Hg contents than those from reference wetlands. Taken together, these data suggest a shift toward lower trophic levels and a possible reduction in mercury methylation in impacted wetlands. Our study provides clear evidence that hydrological modification and land-use change in the Everglades have changed the system from one driven primarily by in-situ productivity to one that is partially dependent on allochthonous carbon input from peat soils in the agricultural area and altered the Hg biogeochemical cycle in the wetlands. The results have

  20. The effect of warming on grassland evapotranspiration partitioning using laser-based isotope monitoring techniques

    KAUST Repository

    Wang, Lixin

    2013-06-01

    The proportion of transpiration (T) in total evapotranspiration (ET) is an important parameter that provides insight into the degree of biological influence on the hydrological cycles. Studies addressing the effects of climatic warming on the ecosystem total water balance are scarce, and measured warming effects on the T/ET ratio in field experiments have not been seen in the literature. In this study, we quantified T/ET ratios under ambient and warming treatments in a grassland ecosystem using a stable isotope approach. The measurements were made at a long-term grassland warming site in Oklahoma during the May-June peak growing season of 2011. Chamber-based methods were used to estimate the δ2H isotopic composition of evaporation (δE), transpiration (δT) and the aggregated evapotranspiration (δET). A modified commercial conifer leaf chamber was used for δT, a modified commercial soil chamber was used for δE and a custom built chamber was used for δET. The δE, δET and δT were quantified using both the Keeling plot approach and a mass balance method, with the Craig-Gordon model approach also used to calculate δE. Multiple methods demonstrated no significant difference between control and warming plots for both δET and δT. Though the chamber-based estimates and the Craig-Gordon results diverged by about 12‰, all methods showed that δE was more depleted in the warming plots. This decrease in δE indicates that the evaporation flux as a percentage of total water flux necessarily decreased for δET to remain constant, which was confirmed by field observations. The T/ET ratio in the control treatment was 0.65 or 0.77 and the ratio found in the warming treatment was 0.83 or 0.86, based on the chamber method and the Craig-Gordon approach. Sensitivity analysis of the Craig-Gordon model demonstrates that the warming-induced decrease in soil liquid water isotopic composition is the major factor responsible for the observed δE depletion and the temperature

  1. Measurements of Volatile Circumstellar Isotopes: Effects of Fractionation vs. Nucleosynthesis

    Science.gov (United States)

    Milam, Stefanie

    The origin, evolution, and fate of our Universe and/or Galaxy have puzzled humankind for centuries. One approach to answering this question is to gain further understanding of stellar evolution, since stars are fundamental in galaxy development and evolution. A compilation of stellar composition can reveal the age, dynamics, and possibly the evolutionary state of a galaxy. In particular the volatile isotope ratios carry an imprint of stellar evolution and nucleosynthesis. Primitive materials, such as meteorites and IDPs, have revealed a component of ``atypical" isotopic signatures of these fundamental elements denoting a possible stellar origin. Understanding the processes by which these elements derive is essential for astrophysics on cosmochemical, galactic, stellar, and planetary scales. We propose to analyze data obtained from the Herschel Space Observatory of circumstellar envelopes to definitively measure C, N, and O isotope ratios and test current models of photo-selective isotope fractionation vs. nucleosynthetically determined values. This proposal augments data from the Herschel Space Observatory, primarily from the HIFISTARS program and MESS, though the entire Herschel archive will be searched for relevant data. The broader implications for this study include fundamental data necessary for furthering our current understanding of stellar nucleosynthesis, circumstellar chemistry, Galactic chemical evolution, and the origin of presolar grains found in primitive materials. We will focus on isotopologues of species formed in thermochemical equilibrium and trace their natal, nucleosynthetic isotope ratios. We will analyze Herschel data obtained for a survey of evolved stars with varying degrees of nuclear processing, evolutionary states, and envelope chemistry (e.g. oxygen-rich vs. carbon-rich). A full circumstellar model will be developed for each source to address specific affects that may influence either the ratios or chemistry. The isotope ratios of 12C

  2. Effectiveness of different pre-treatments in recovering pre-burial isotopic ratios of charred plants.

    Science.gov (United States)

    Brinkkemper, O; Braadbaart, F; van Os, B; van Hoesel, A; van Brussel, A A N; Fernandes, R

    2018-02-15

    Isotopic analysis of archaeological charred plant remains offers useful archaeological information. However, adequate sample pre-treatment protocols may be necessary to provide a contamination-free isotopic signal while limiting sample loss and achieving a high throughput. Under these constraints, research was undertaken to compare the performance of different pre-treatment protocols. Charred archaeological plant material was selected for isotopic analysis (δ 13 C and δ 15 N values) by isotope ratio mass spectrometry from a variety of plant species, time periods and soil conditions. Preservation conditions and the effectiveness of cleaning protocols were assessed through Fourier transform infrared spectroscopy and X-ray fluorescence (XRF) spectrometry. An acid-base-acid protocol, successfully employed in radiocarbon dating, was used to define a contamination-free isotopic reference. Acid-base-acid isotopic measurements were compared with those obtained from untreated material and an acid-only protocol. The isotopic signals of untreated material and the acid-only protocol typically did not differ more than 1‰ from those of the acid-base-acid reference. There were no significant isotopic offsets between acid-base-acid and acid-only or untreated samples. Sample losses in the acid-base-acid protocol were on average 50 ± 17% (maximum = 98.4%). Elemental XRF measurements showed promising results in the detection of more contaminated samples albeit with a high rate of false positives. For the large range of preservation conditions described in the study, untreated charred plant samples, water cleaned of sediments, provide reliable stable isotope ratios of carbon and nitrogen. The use of pre-treatments may be necessary under different preservation conditions or more conservative measurement uncertainties should be reported. Copyright © 2017 John Wiley & Sons, Ltd.

  3. Evidence for dipolar bands in mercury isotopes using EUROGAM multi-detector

    International Nuclear Information System (INIS)

    Le Coz, Y.

    1995-01-01

    This thesis is devoted to the study of nuclear structure around mass A 190 and in particular, to the search of oblate rotational dipole bands in mercury isotopes. The reactions used to populate high spin states in 192 Hg and 193 Hg were 160 Gd ( 36 S,n) 192 Hg and 150 Nd( 48 Ca, 5n) 193 Hg at beam energies of 159 and 213 MeV. Gamma-rays have been detected using the EUROGAM phase I array. Level schemes of those two nuclei have been extended up to an excitation energy of about 10 MeV and approximately spin 35h. In 192 Hg, two new dipole bands have been observed. Those two structures, as well as two similar structures in 193 Hg, have been connected to the low-lying states; so, excitation energy and bandhead spin of those bands have been deduced. Angular distribution and correlation analysis (specific to EUROGRAM phase I) have confirmed that the transitions are dipoles. After a general presentation of dipole bands in this A = 190 mass region, experimental results are compared with mean-field Hartree-Fock + BCS calculations, using the rotor plus quasi-particles model. The results are consistent with weakly oblate structures based on configurations which involve high-K proton orbitals driving the nucleus to an oblate shape. (author). 81 refs., 47 figs., 8 tabs., 4 ann

  4. Uranium isotope evidence for two episodes of deoxygenation during Oceanic Anoxic Event 2

    Science.gov (United States)

    Clarkson, Matthew O.; Stirling, Claudine H.; Jenkyns, Hugh C.; Dickson, Alexander J.; Porcelli, Don; Moy, Christopher M.; Pogge von Strandmann, Philip A. E.; Cooke, Ilsa R.; Lenton, Timothy M.

    2018-03-01

    Oceanic Anoxic Event 2 (OAE 2), occurring ˜94 million years ago, was one of the most extreme carbon cycle and climatic perturbations of the Phanerozoic Eon. It was typified by a rapid rise in atmospheric CO2, global warming, and marine anoxia, leading to the widespread devastation of marine ecosystems. However, the precise timing and extent to which oceanic anoxic conditions expanded during OAE 2 remains unresolved. We present a record of global ocean redox changes during OAE 2 using a combined geochemical and carbon cycle modeling approach. We utilize a continuous, high-resolution record of uranium isotopes in pelagic and platform carbonate sediments to quantify the global extent of seafloor anoxia during OAE 2. This dataset is then compared with a dynamic model of the coupled global carbon, phosphorus, and uranium cycles to test hypotheses for OAE 2 initiation. This unique approach highlights an intra-OAE complexity that has previously been underconstrained, characterized by two expansions of anoxia separated by an episode of globally significant reoxygenation coincident with the “Plenus Cold Event.” Each anoxic expansion event was likely driven by rapid atmospheric CO2 injections from multiphase Large Igneous Province activity.

  5. Isotopic evidence for extraterrestrial non-racemic amino acids in the Murchison meteorite.

    Science.gov (United States)

    Engel, M H; Macko, S A

    1997-09-18

    Many amino acids contain an asymmetric centre, occurring as laevorotatory, L, or dextrorotatory, D, compounds. It is generally assumed that abiotic synthesis of amino acids on the early Earth resulted in racemic mixtures (L- and D-enantiomers in equal abundance). But the origin of life required, owing to conformational constraints, the almost exclusive selection of either L- or D-enantiomers, and the question of why living systems on the Earth consist of L-enantiomers rather than D-enantiomers is unresolved. A substantial fraction of the organic compounds on the early Earth may have been derived from comet and meteorite impacts. It has been reported previously that amino acids in the Murchison meteorite exhibit an excess of L-enantiomers, raising the possibility that a similar excess was present in the initial inventory of organic compounds on the Earth. The stable carbon isotope compositions of individual amino acids in Murchison support an extraterrestrial origin -- rather than a terrestrial overprint of biological amino acids-although reservations have persisted. Here we show that individual amino-acid enantiomers from Murchison are enriched in 15N relative to their terrestrial counterparts, so confirming an extraterrestrial source for an L-enantiomer excess in the Solar System that may predate the origin of life on the Earth.

  6. Isotopic evidence for an early shift to C₄ resources by Pliocene hominins in Chad.

    Science.gov (United States)

    Lee-Thorp, Julia; Likius, Andossa; Mackaye, Hassane T; Vignaud, Patrick; Sponheimer, Matt; Brunet, Michel

    2012-12-11

    Foods derived from C(4) plants were important in the dietary ecology of early Pleistocene hominins in southern and eastern Africa, but the origins and geographic variability of this relationship remain unknown. Carbon isotope data show that Australopithecus bahrelghazali individuals from Koro Toro in Chad are significantly enriched in (13)C, indicating a dependence on C(4) resources. As these sites are over 3 million years in age, the results extend the pattern of C(4) dependence seen in Paranthropus boisei in East Africa by more than 1.5 million years. The Koro Toro hominin fossils were found in argillaceous sandstone levels along with abundant grazing and aquatic faunal elements that, in combination, indicate the presence of open to wooded grasslands and stream channels associated with a greatly enlarged Lake Chad. In such an environment, the most abundant C(4) plant resources available to A. bahrelghazali were grasses and sedges, neither of which is usually considered as standard great ape fare. The results suggest an early and fundamental shift in hominin dietary ecology that facilitated the exploitation of new habitats.

  7. Isotopic evidence for an early shift to C4 resources by Pliocene hominins in Chad

    Science.gov (United States)

    Lee-Thorp, Julia; Likius, Andossa; Mackaye, Hassane T.; Vignaud, Patrick; Sponheimer, Matt; Brunet, Michel

    2012-01-01

    Foods derived from C4 plants were important in the dietary ecology of early Pleistocene hominins in southern and eastern Africa, but the origins and geographic variability of this relationship remain unknown. Carbon isotope data show that Australopithecus bahrelghazali individuals from Koro Toro in Chad are significantly enriched in 13C, indicating a dependence on C4 resources. As these sites are over 3 million years in age, the results extend the pattern of C4 dependence seen in Paranthropus boisei in East Africa by more than 1.5 million years. The Koro Toro hominin fossils were found in argillaceous sandstone levels along with abundant grazing and aquatic faunal elements that, in combination, indicate the presence of open to wooded grasslands and stream channels associated with a greatly enlarged Lake Chad. In such an environment, the most abundant C4 plant resources available to A. bahrelghazali were grasses and sedges, neither of which is usually considered as standard great ape fare. The results suggest an early and fundamental shift in hominin dietary ecology that facilitated the exploitation of new habitats. PMID:23150583

  8. First molecular and isotopic evidence of millet processing in prehistoric pottery vessels

    Science.gov (United States)

    Heron, Carl; Shoda, Shinya; Breu Barcons, Adrià; Czebreszuk, Janusz; Eley, Yvette; Gorton, Marise; Kirleis, Wiebke; Kneisel, Jutta; Lucquin, Alexandre; Müller, Johannes; Nishida, Yastami; Son, Joon-Ho; Craig, Oliver E.

    2016-12-01

    Analysis of organic residues in pottery vessels has been successful in detecting a range of animal and plant products as indicators of food preparation and consumption in the past. However, the identification of plant remains, especially grain crops in pottery, has proved elusive. Extending the spectrum is highly desirable, not only to strengthen our understanding of the dispersal of crops from centres of domestication but also to determine modes of food processing, artefact function and the culinary significance of the crop. Here, we propose a new approach to identify millet in pottery vessels, a crop that spread throughout much of Eurasia during prehistory following its domestication, most likely in northern China. We report the successful identification of miliacin (olean-18-en-3β-ol methyl ether), a pentacyclic triterpene methyl ether that is enriched in grains of common/broomcorn millet (Panicum miliaceum), in Bronze Age pottery vessels from the Korean Peninsula and northern Europe. The presence of millet is supported by enriched carbon stable isotope values of bulk charred organic matter sampled from pottery vessel surfaces and extracted n-alkanoic acids, consistent with a C4 plant origin. These data represent the first identification of millet in archaeological ceramic vessels, providing a means to track the introduction, spread and consumption of this important crop.

  9. Isotopic evidence for extraterrestrial non- racemic amino acids in the Murchison meteorite

    Science.gov (United States)

    Engel, M. H.; Macko, S. A.

    1997-09-01

    Many amino acids contain an asymmetric centre, occurring as laevorotatory, L, or dextrorotatory, D, compounds. It is generally assumed that abiotic synthesis of amino acids on the early Earth resulted in racemic mixtures (L- and D-enantiomers in equal abundance). But the origin of life required, owing to conformational constraints, the almost exclusive selection of either L- or D-enantiomers, and the question of why living systems on the Earth consist of L-enantiomers rather than D-enantiomers is unresolved. A substantial fraction of the organic compounds on the early Earth may have been derived from comet and meteorite impacts. It has been reported previously that amino acids in the Murchison meteorite exhibit an excess of L-enantiomers, raising the possibility that a similar excess was present in the initial inventory of organic compounds on the Earth. The stable carbon isotope compositions of individual amino acids in Murchison support an extraterrestrial origin-rather than a terrestrial overprint of biological amino acids-although reservations have persisted (see, for example, ref. 9). Here we show that individual amino-acid enantiomers from Murchison are enriched in 15N relative to their terrestrial counterparts, so confirming an extraterrestrial source for an L-enantiomer excess in the Solar System that may predate the origin of life on the Earth.

  10. The trophic and metabolic pathways of foraminifera in the Arabian Sea: evidence from cellular stable isotopes

    Science.gov (United States)

    Jeffreys, R. M.; Fisher, E. H.; Gooday, A. J.; Larkin, K. E.; Billett, D. S. M.; Wolff, G. A.

    2015-03-01

    The Arabian Sea is a region of elevated productivity with the highest globally recorded fluxes of particulate organic matter (POM) to the deep ocean, providing an abundant food source for fauna at the seafloor. However, benthic communities are also strongly influenced by an intense oxygen minimum zone (OMZ), which impinges on the continental slope from 100 to 1000 m water depth. We compared the trophic ecology of foraminifera on the Oman and Pakistan margins of the Arabian Sea (140-3185 m water depth). These two margins are contrasting both in terms of the abundance of sedimentary organic matter and the intensity of the OMZ. Organic carbon concentrations of surficial sediments were higher on the Oman margin (3.32 ± 1.4%) compared to the Pakistan margin (2.45 ± 1.1%) and sedimentary organic matter (SOM) quality estimated from the Hydrogen Index was also higher on the Oman margin (300-400 mg HC mg TOC-1) compared to the Pakistan margin (responsible for the differences observed in foraminiferal isotopic composition. In addition, at the time of sampling, whole jellyfish carcasses (Crambionella orsini) and a carpet of jelly detritus were observed across the Oman margin transect. Associated chemosynthetic bacteria may have provided an organic-rich food source for foraminifera at these sites. Our data suggest that foraminifera in OMZ settings can utilise a variety of food sources and metabolic pathways to meet their energetic demands.

  11. Lithium isotope effect in the extraction systems of polyethers: effect of salt concentration

    International Nuclear Information System (INIS)

    Fang Shengqiang; Fu Lian

    1991-01-01

    Separation factors of lithium isotopes at 20 deg C were determined in the extraction systems of B15C5-CHCl 3 /LiBr-H 2 O. The initial concentration of LiBr was controlled in the extent of more than 2 mol/l. It may be established that the increase of LiBr concentration causes a remarkable increase of the separation factor. The essence of this effect due to the change in salt concentration was discussed in connection with examination of relevant phenomena in literature. It can be concluded that the relationship between α and Cm, the concentration of lithium salt, is dependent on K Q and K P express respectively, lithium isotope exchange equilibrium constants between Li-crownether complex and hydrated lithium ion for lithium concentration less than 1-2 mol/l, and between lithium salt ion pair and hydrated lithium ion for lithium concentration more than 2 mol/l in aqueous phase

  12. Direct determination of equilibrium deuterium isotope effects at natural abundance

    International Nuclear Information System (INIS)

    Zhang, B.; Martin, M.L.

    1992-01-01

    A great variety of techniques has been used to study deuterium-protium partitioning in exchanging systems at equilibrium. In this context it is shown that the determination of site-specific isotope contents by 2 H-NMR at natural abundance provides simple and direct access to thermodynamic isotope fractionation factors. This method avoids the recourse to deuterated species and therefore the approximations inherent in the analysis of complex isotopomeric mixtures. A number of slowly exchanging systems involving OH, NH, or SH groups and water offer suitable conditions (large chemical shift differences, moderate line widths,hor-ellipsis) for the relatively accurate determination of thermodynamic fractionation factors. Moreover multiple fractionations can be observed and compared in ternary mixtures. 25 refs., 2 tabs

  13. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

    Science.gov (United States)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.

    2014-09-01

    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called ;heavy group;), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (;equilibrium group;). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (;light group;), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the ;carbonate ion effect;. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only ;apparent;, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate

  14. [Evidence of dermatological effects of chamomile].

    Science.gov (United States)

    Rügge, Simone Danty; Nielsen, Maiken; Jacobsen, Andreas Skovgård; Vang, Ole; Jemec, Gregor B E

    2010-12-13

    Recent years have seen a rise in the demand for dermatological herbal and plant products as well as products containing chamomile. Extracts and decoctions made from this plant are often recommended by laymen for treatment of a number of skin diseases e.g. inflammation, wounds and itching. This systematic review explores the evidence base of the dermatological effects of chamomile. While numerous beneficial effects of chamomile have been suggested no studies have so far been able to substantiate these claims significantly. The absence of evidence is primarily caused by the design and quality of the studies identified.

  15. Multiple isotope effects with alternative dinucleotide substrates as a probe of the malic enzyme reaction

    International Nuclear Information System (INIS)

    Weiss, P.M.; Urbauer, J.L.; Cleland, W.W.; Gavva, S.R.; Harris, B.G.; Cook, P.F.

    1991-01-01

    Deuterium isotope effects and 13 C isotope effects with deuterium- and protium-labeled malate have been obtained for both NAD- and NADP-malic enzymes by using a variety of alternative dinucleotide substrates. With nicotinamide-containing dinucleotides as the oxidizing substrate, the 13 C effect decreases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data are consistent with a stepwise chemical mechanism in which hydride transfer precedes decarboxylation of the oxalacetate intermediate as previously proposed. When dinucleotide substrates such as thio-NAD, 3-nicotinamide rings are used, the 13 C effect increases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data, at face value, are consistent with a change in mechanism from stepwise to concerted for the oxidative decarboxylation portion of the mechanism. However, the increase in the deuterium isotope effect from 1.5 to 3 with a concomitant decrease in the 13 C isotope effect from 1.034 to 1.003 as the dinucleotide substrate is changed suggests that the reaction may still be stepwise with the non-nicotinamide dinucleotides. A more likely explanation is that a β-secondary 13 C isotope effect accompanies hydride transfer as a result of hyperconjugation of the β-carboxyl of malate as the transition state for the hydride transfer step is approached

  16. Stable isotope and DNA evidence for ritual sequences in Inca child sacrifice

    DEFF Research Database (Denmark)

    Wilson, Andrew S; Taylor, Timothy; Ceruti, Maria Constanza

    2007-01-01

    Four recently discovered frozen child mummies from two of the highest peaks in the south central Andes now yield tantalizing evidence of the preparatory stages leading to Inca ritual killing as represented by the unique capacocha rite. Our interdisciplinary study examined hair from the mummies...

  17. Uranium isotope evidence for an expansion of marine anoxia during the end-Triassic extinction

    Science.gov (United States)

    Jost, Adam B.; Bachan, Aviv; van de Schootbrugge, Bas; Lau, Kimberly V.; Weaver, Karrie L.; Maher, Kate; Payne, Jonathan L.

    2017-08-01

    The end-Triassic extinction coincided with an increase in marine black shale deposition and biomarkers for photic zone euxinia, suggesting that anoxia played a role in suppressing marine biodiversity. However, global changes in ocean anoxia are difficult to quantify using proxies for local anoxia. Uranium isotopes (δ238U) in CaCO3 sediments deposited under locally well-oxygenated bottom waters can passively track seawater δ238U, which is sensitive to the global areal extent of seafloor anoxia due to preferential reduction of 238U(VI) relative to 235U(VI) in anoxic marine sediments. We measured δ238U in shallow-marine limestones from two stratigraphic sections in the Lombardy Basin, northern Italy, spanning over 400 m. We observe a ˜0.7‰ negative excursion in δ238U beginning in the lowermost Jurassic, coeval with the onset of the initial negative δ13C excursion and persisting for the duration of subsequent high δ13C values in the lower-middle Hettangian stage. The δ238U excursion cannot be realistically explained by local mixing of uranium in primary marine carbonate and reduced authigenic uranium. Based on output from a forward model of the uranium cycle, the excursion is consistent with a 40-100-fold increase in the extent of anoxic deposition occurring worldwide. Additionally, relatively constant uranium concentrations point toward increased uranium delivery to the oceans from continental weathering, which is consistent with weathering-induced eutrophication following the rapid increase in pCO2 during emplacement of the Central Atlantic Magmatic Province. The relative timing and duration of the excursion in δ238U implies that anoxia could have delayed biotic recovery well into the Hettangian stage.

  18. Boron isotope evidence for oceanic carbon dioxide leakage during the last deglaciation.

    Science.gov (United States)

    Martínez-Botí, M A; Marino, G; Foster, G L; Ziveri, P; Henehan, M J; Rae, J W B; Mortyn, P G; Vance, D

    2015-02-12

    Atmospheric CO2 fluctuations over glacial-interglacial cycles remain a major challenge to our understanding of the carbon cycle and the climate system. Leading hypotheses put forward to explain glacial-interglacial atmospheric CO2 variations invoke changes in deep-ocean carbon storage, probably modulated by processes in the Southern Ocean, where much of the deep ocean is ventilated. A central aspect of such models is that, during deglaciations, an isolated glacial deep-ocean carbon reservoir is reconnected with the atmosphere, driving the atmospheric CO2 rise observed in ice-core records. However, direct documentation of changes in surface ocean carbon content and the associated transfer of carbon to the atmosphere during deglaciations has been hindered by the lack of proxy reconstructions that unambiguously reflect the oceanic carbonate system. Radiocarbon activity tracks changes in ocean ventilation, but not in ocean carbon content, whereas proxies that record increased deglacial upwelling do not constrain the proportion of upwelled carbon that is degassed relative to that which is taken up by the biological pump. Here we apply the boron isotope pH proxy in planktic foraminifera to two sediment cores from the sub-Antarctic Atlantic and the eastern equatorial Pacific as a more direct tracer of oceanic CO2 outgassing. We show that surface waters at both locations, which partly derive from deep water upwelled in the Southern Ocean, became a significant source of carbon to the atmosphere during the last deglaciation, when the concentration of atmospheric CO2 was increasing. This oceanic CO2 outgassing supports the view that the ventilation of a deep-ocean carbon reservoir in the Southern Ocean had a key role in the deglacial CO2 rise, although our results allow for the possibility that processes operating in other regions may also have been important for the glacial-interglacial ocean-atmosphere exchange of carbon.

  19. Radioactive Emissions from Fission-Based Medical Isotope Production and Their Effect on Global Nuclear Explosion Detection

    International Nuclear Information System (INIS)

    Bowyer, T.; Saey, P.

    2015-01-01

    The use of medical isotopes, such as Tc-99m, is widespread with over 30 million procedures being performed every year, but the fission-based production of isotopes used for medical procedures causes emissions into the environment. This paper will show that gaseous radioactive isotopes of xenon, such as Xe-133, are released in high quantities, because they have a high fission cross section and they are difficult to scrub from the processes used to produce the medical isotopes due to their largely unreactive nature. Unfortunately, the reasons that large amounts of radioactive xenon isotopes are emitted from isotope production are the same as those that make these isotopes the most useful isotopes for the detection of underground nuclear explosions. Relatively recently, the nuclear explosion monitoring community has established a provisional monitoring network for the Comprehensive Nuclear-Test-Ban Treaty (CTBT) that includes radioactive xenon monitoring as a major component. This community has discovered that emissions from medical isotope production present a more serious problem to nuclear explosion monitoring than thought when the network was first conceived. To address the growing problem, a group of scientists in both the monitoring and the isotope production communities have come together to attempt to find scientific and pragmatic ways to address the emissions problems, recognizing that medical isotope production should not be adversely affected, while monitoring for nuclear explosions should remain effective as isotope production grows, changes, and spreads globally. (author)

  20. Isotope effect study of κ-(BEDT-TTF)2Cu(NCS)2: Labeling in the anion

    International Nuclear Information System (INIS)

    Kini, A.M.; Wang, H.H.; Schlueter, J.A.

    1995-01-01

    Since the initial discovery of organic superconductivity in 1979, a large number of organic superconductors have now been synthesized. However, the mechanism of electron-pairing in these novel superconductors has remained largely unresolved. Isotope effect studies constitute an important experimental tool for the investigation of whether or not the electron-pairing mechanism in organic superconductors is phonon-mediated, as in conventional superconductors. Recent isotope effect studies in the authors' laboratory, involving seven different isotopically labeled BEDT-TTF (or ET) derivatives, have demonstrated the following: (1) intramolecular phonon modes involving C double-bond C and Csingle bondS stretching vibrations in the ET donor molecule are not the dominant mediators of electron-pairing, and (2) in κ-(ET) 2 Cu(NCS) 2 , there exist two competing isotope effects--a normal mass effect, i.e., lowering of T c upon isotopic labeling, when the ET molecular mass is increased by concurrent 13 C and 34 S labeling, in addition to an inverse isotope effect upon deuterium labeling in ET. It is of great interest to investigate if there is an isotope effect when the charge-compensating anions, which are also located within the non-conducting layer in the superconducting cation-radical salts, are isotopically labeled. The existence of an isotope effect when the anions are labeled would be indicative of electron-pairing with the mediation of vibrational frequencies associated with the anions. In this paper, the authors present the results of the first isotope effect study in which isotopic labeling in the anion portion of κ-(ET) 2 Cu(NCS) 2 is carried out. The authors find no isotope effect when the carbon and nitrogen atoms of the thiocyanate groups in the anion are replaced with 13 C and 15 N isotopes

  1. Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field, California

    Science.gov (United States)

    Bacon, C.R.; Kurasawa, H.; Delevaux, M.H.; Kistler, R.W.; Doe, B.R.

    1984-01-01

    The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (87Sr/86Sr=0.7036,206Pb/204Pb=19.05,207Pb/204Pb=15.62,208Pb/204Pb= 38.63). The (initial) isotopic composition of typical rhyolite (87Sr/86Sr=0.7053,206Pb/204Pb=19.29,207Pb/204Pb= 15.68,208Pb/204Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs. ?? 1984 Springer-Verlag.

  2. Evidence for a mantle component shown by rare gases, C and N isotopes in polycrystalline diamonds from Orapa (Botswana) [rapid communication

    Science.gov (United States)

    Gautheron, Cécile; Cartigny, Pierre; Moreira, Manuel; Harris, Jeff. W.; Allègre, Claude J.

    2005-12-01

    In an attempt to constrain the origin of polycrystalline diamond, combined analyses of rare gases and carbon and nitrogen isotopes were performed on six such diamonds from Orapa (Botswana). Helium shows radiogenic isotopic ratios of R/Ra = 0.14-1.29, while the neon ratios ( 21Ne/ 22Ne of up to 0.0534) reflect a component from mantle, nucleogenic and atmospheric sources. 40Ar/ 36Ar ratios of between 477 and 6056 are consistent with this interpretation. The ( 129Xe/ 130Xe) isotopic ratios range between 6.54 and 6.91 and the lower values indicate an atmospheric component. The He, Ne, Ar and Xe isotopic compositions and the Xe isotopic pattern are clear evidence for a mantle component rather than a crustal one in the source of the polycrystalline diamonds from Orapa. The δ 13C and δ 15N isotopic values of - 1.04 to - 9.79‰ and + 4.5 to + 15.5‰ respectively, lie within the range of values obtained from the monocrystalline diamonds at that mine. Additionally, this work reveals that polycrystalline diamonds may not be the most appropriate samples to study if the aim is to consider the compositional evolution of rare gases through time. Our data shows that after crystallization, the polycrystalline diamonds undergo both gas loss (that is more significant for the lighter rare gases such as He and Ne) and secondary processes (such as radiogenic, nucleogenic and fissiogenic, as well as atmospheric contamination). Finally, if polycrystalline diamonds sampled an old mantle (1-3.2 Ga), the determined Xe isotopic signatures, which are similar to present MORB mantle - no fissiogenic Xe from fission of 238U being detectable - imply either that Xe isotopic ratios have not evolved within the convective mantle since diamond crystallization, or that these diamonds are actually much younger.

  3. Chemical Ligation and Isotope Labeling to Locate Dynamic Effects during Catalysis by Dihydrofolate Reductase.

    Science.gov (United States)

    Luk, Louis Y P; Ruiz-Pernía, J Javier; Adesina, Aduragbemi S; Loveridge, E Joel; Tuñón, Iñaki; Moliner, Vincent; Allemann, Rudolf K

    2015-07-27

    Chemical ligation has been used to alter motions in specific regions of dihydrofolate reductase from E. coli and to investigate the effects of localized motional changes on enzyme catalysis. Two isotopic hybrids were prepared; one with the mobile N-terminal segment containing heavy isotopes ((2) H, (13) C, (15) N) and the remainder of the protein with natural isotopic abundance, and the other one with only the C-terminal segment isotopically labeled. Kinetic investigations indicated that isotopic substitution of the N-terminal segment affected only a physical step of catalysis, whereas the enzyme chemistry was affected by protein motions from the C-terminal segment. QM/MM studies support the idea that dynamic effects on catalysis mostly originate from the C-terminal segment. The use of isotope hybrids provides insights into the microscopic mechanism of dynamic coupling, which is difficult to obtain with other studies, and helps define the dynamic networks of intramolecular interactions central to enzyme catalysis. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  4. Isotope effects in the evaporation of water: a status report of the Craig-Gordon model.

    Science.gov (United States)

    Horita, Juske; Rozanski, Kazimierz; Cohen, Shabtai

    2008-03-01

    The Craig-Gordon model (C-G model) [H. Craig, L.I. Gordon. Deuterium and oxygen 18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperatures, E. Tongiorgi (Ed.), pp. 9-130, Laboratorio di Geologia Nucleare, Pisa (1965).] has been synonymous with the isotope effects associated with the evaporation of water from surface waters, soils, and vegetations, which in turn constitutes a critical component of the global water cycle. On the occasion of the four decades of its successful applications to isotope geochemistry and hydrology, an attempt is made to: (a) examine its physical background within the framework of modern evaporation models, (b) evaluate our current knowledge of the environmental parameters of the C-G model, and (c) comment on a general strategy for the use of these parameters in field applications. Despite its simplistic representation of evaporation processes at the water-air interface, the C-G model appears to be adequate to provide the isotopic composition of the evaporation flux. This is largely due to its nature for representing isotopic compositions (a ratio of two fluxes of different isotopic water molecules) under the same environmental conditions. Among many environmental parameters that are included in the C-G model, accurate description and calculations are still problematic of the kinetic isotope effects that occur in a diffusion-dominated thin layer of air next to the water-air interface. In field applications, it is of importance to accurately evaluate several environmental parameters, particularly the relative humidity and isotopic compositions of the 'free-atmosphere', for a system under investigation over a given time-scale of interest (e.g., hourly to daily to seasonally). With a growing interest in the studies of water cycles of different spatial and temporal scales, including paleoclimate and water resource studies, the importance and utility of the C-G model is also likely to

  5. Isotopic Evidence For The Primary Production, Provenance And Trade Of Late Bronze Age Glass In The Mediterranean.

    Science.gov (United States)

    Henderson, J.; Evans, J.; Nikita, K.

    The earliest known man made glass comes from Mesopotamia and dates to the 23rd century BC. By the 16th century BC the first glass vessels appear in Mesopotamia, but the earliest evidence for the fusion of glass from raw materials has been found at the 13th century BC Egyptian site of Qantir. Chemical analyses of this elite Late Bronze Age material have produced compositional distinctions between glasses found in Mesopotamia and Egypt. It is however debatable whether trace element concentrations provide a (geological) provenance for the glasses. By using neodymium and strontium isotopes to fingerprint well-dated chemically analysed 15th to 11th century BC glass samples, we show that independent primary production probably occurred in both Egypt and Mesopotamia in the 14th century BC, and that both of these areas exported glass to Greece. We also discuss the technological implications for glass manufacture and colouring that these new data provide. The results add significant new scientific evidence for glass trade between Late Bronze Age palatial societies. Moreover, it is the first time that this methodology has been used to investigate Bronze Age glass.

  6. Evidence for mass-independent and mass-dependent fractionation of the stable isotopes of mercury by natural processes in aquatic ecosystems

    International Nuclear Information System (INIS)

    Jackson, Togwell A.; Whittle, D. Michael; Evans, Marlene S.; Muir, Derek C.G.

    2008-01-01

    Isotopic and chemical analyses were performed on crustaceans, forage fish, top predator fish, and sediment cores from Lake Ontario and two boreal forest lakes to investigate fractionation of the stable isotopes of Hg in aquatic ecosystems. Multicollector inductively coupled mass spectrometry was used to determine Hg isotope abundances. The Hg isotope data for all three lakes showed mass-independent variation in the organisms but only mass-dependent variation in the sediments. The mass-independent isotope effect was characterised by (1) selective enrichment in isotopes of odd mass number ( 199 Hg and 201 Hg), (2) enrichment in 201 Hg relative to 199 Hg, (3) an inverse relationship between isotopes of odd and even mass number in fish, and (4) a positive correlation with methylHg (CH 3 Hg + ) concentration, and hence with trophic level (although lake whitefish were consistently anomalous, possibly owing to biochemical demethylation). Isotope signatures of species at the same trophic level varied with habitat and diet, differentiating between planktonic and benthic crustaceans and their predators, and between fish that frequent deep, cold water and fish of similar diet that prefer warmer, shallower water, because of corresponding differences in CH 3 Hg + and inorganic Hg content. Isotopic analysis of CH 3 Hg + and inorganic Hg extracted from lake trout proved that the mass-independent isotope effect was due to anomalously high abundances of 199 Hg and 201 Hg in CH 3 Hg + , as implied by the data for whole organisms, suggesting mass-independent fractionation during microbial methylation of Hg. The purely mass-dependent variation in the sediments is attributable to the fact that Hg in sediments is mostly inorganic. The mass-independent fractionation of Hg isotopes can be explained by effects of nuclear spin or nuclear field shift, or both, and penetration of the inner electron shells of Hg by valence electrons of Hg-binding ligands. The results of the research

  7. Predictive Framework and Experimental Tests of the Kinetic Isotope Effect at Redox-Active Interfaces

    Science.gov (United States)

    Kavner, A.; John, S.; Black, J. R.

    2013-12-01

    Electrochemical reactions provide a compelling framework to study kinetic isotope effects because redox-related processes are important for a wide variety of geological and environmental processes. In the laboratory, electrochemical reaction rates can be electronically controlled and measured in the laboratory using a potentiostat. This enables variation of redox reactions rates independent of changes in chemistry and, and the resulting isotope compositions of reactants and products can be separated and analyzed. In the past years, a series of experimental studies have demonstrated a large, light, and tunable kinetic isotope effect during electrodeposition of metal Fe, Zn, Li, Cu, and Mo from a variety of solutions (e.g. Black et al., 2009, 2010, 2011). A theoretical framework based on Marcus kinetic theory predicts a voltage-dependent kinetic isotope effect (Kavner et al., 2005, 2008), however while this framework was able to predict the tunable nature of the effect, it was not able to simultaneously predict absolute reaction rates and relative isotope rates. Here we present a more complete development of a statistical mechanical framework for simple interfacial redox reactions, which includes isotopic behavior. The framework is able to predict a kinetic isotope effect as a function of temperature and reaction rate, starting with three input parameters: a single reorganization energy which describes the overall kinetics of the electron transfer reaction, and the equilibrium reduced partition function ratios for heavy and light isotopes in the product and reactant phases. We show the framework, elucidate some of the predictions, and show direct comparisons against isotope fractionation data obtained during laboratory and natural environment redox processes. A. Kavner, A. Shahar, F. Bonet, J. Simon and E. Young (2005) Geochim. Cosmochim. Acta, 69(12), 2971-2979. A. Kavner, S. G. John, S. Sass, and E. A. Boyle (2008), Geochim. Cosmochim. Acta, vol 72, pp. 1731

  8. Ab Initio Calculations of Deuterium Isotope Effects on Chemical Shifts of Salt-Bridged Lysines

    DEFF Research Database (Denmark)

    Ullah, Saif; Ishimoto, Takayoshi; Williamson, Mike P.

    2011-01-01

    Deuterium isotope effects measure the change in chemical shift on substitution of a proton by deuterium. They have been calculated by direct treatment of the H/D nuclear quantum effect using a multicomponent ab initio molecular orbital method based on a non-Born−Oppenheimer approximation. This me......Deuterium isotope effects measure the change in chemical shift on substitution of a proton by deuterium. They have been calculated by direct treatment of the H/D nuclear quantum effect using a multicomponent ab initio molecular orbital method based on a non-Born−Oppenheimer approximation...

  9. The effect of the isotopic composition of oxygen on the non-mass-dependent isotopic fractionation in the formation of ozone by discharge of O2. [from meteorites

    Science.gov (United States)

    Yang, Jongmann; Epstein, Samuel

    1987-01-01

    Isotopic fractionation processes in the formation of O3 by 20-kV 60-kHz discharge of O2 in a fused silica container at 77 K are investigated experimentally, with a focus on the effects of changes in the isotopic composition of O2, the O2 pressure, the degree of O3 formation, and the discharge geometry on the isotope abundances in the postdischarge O2 and O3. The results are presented in tables and graphs and compared with the predictions of theoretical models involving vibrational anharmonicity and symmetry effects on O3 predissociation. In experiments using O2 enriched with O-17 and O-18, the heavy isotope is enriched in the residual O2 and not in the O3, whereas the opposite is true when atmospheric isotope abundances are used. It is inferred that the predissociation rate depends on the symmetry and mass of the O3 molecules and not on self-shielding or symmetry effects in the reactant O2. The potential value of the present findings for studies of anomalous isotope abundances in meteorites is indicated.

  10. Isotopic evidence for the formation of unusually humus-rich soils in the Baltic region

    Science.gov (United States)

    Leinweber, Peter; Acksel, Andre; Kühn, Peter

    2017-04-01

    Arable mineral soils in the Pleistocene landscape of Northern Germany usually contain about 4 to 8 kg of organic C (Corg) per m2, most of which is visually recognizable concentrated in the tilled topsoil horizon. Some unusually humus-rich (10 to 20 kg Corg m-2), and deeply (> 70 cm) dark-colored soils in coastal regions with mollic properties have been classified as Chernozems. Their location far away from the middle German and Central European Chernozem regions, absence of steppe vegetation and semi-arid climate conditions make classical pedogenetic theories doubtful. However, non-targeted mass spectrometric analyses of soil organic matter (SOM) composition revealed great similarities with typical Chernozems worldwide (Thiele-Bruhn et al., 2014) and made alternative (e.g. waterlogged) pathways of SOM accumulation unlikely. Subsequent detailed multi-method SOM analyses down the soil profiles revealed relative enrichments in cyclic ("black carbon") and heterocyclic organic compounds in the deeper, bioturbated horizons. These were plausibly explained by the input of combustion residues, likely originating from anthropogenic activities because spots of these soils coincided with archeological artifacts of early settlements (Acksel et al., 2016). However, these finding could not completely explain the genesis of Chernozems in the Baltic region. Therefore, we actually explored isotope analyses (12/13C, 13/14C, 14/15N, 32/34S) to find out the origin of these unusual SOM enrichments and the time period in which it occurred. The results will be compiled to a consistent hypothesis on the formation of these soils in the Baltic and other Northern European regions. References Acksel, A., W. Amelung, P. Kühn, E. Gehrt, T. Regier, P. Leinweber. 2016. Soil organic matter characteristics as indicator of Chernozem genesis in the Baltic Sea region. Geoderma Regional 7, 187-200. Thiele-Bruhn, S., Leinweber P., Eckhardt K.-U., Siem H.K., Blume H.-P. 2014. Identifying Chernozem

  11. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    International Nuclear Information System (INIS)

    Rosenberg, R.M.; O'Leary, M.H.

    1985-01-01

    The authors have measured the 13 C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D 2 O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D 2 O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The 13 C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the 13 C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier

  12. Dew water effects on leaf water using a stable isotope approach

    Science.gov (United States)

    Kim, K.; Lee, X.

    2009-12-01

    The presence of dew is a common meteorological phenomenon in field conditions and takes into account for significant portion of hydrologic processes in terrestrial ecosystems. The isotope composition of leaf water plays an important role in the isotopic water and carbon fluxes between terrestrial plants and the atmosphere. However, the consequence of dew formation in the plant-atmosphere relations has been ignored in many studies. The objective of this study is to improve our understanding of environmental and biological controls on the leaf water in equilibrium with dew water through laboratory experiments. Five species of plants (soybean, corn, sorghum, wheat, cotton) were grown hydroponically with water of a known isotopic content in a greenhouse. On the day of the experiment, they were first moved to ambient environment in full sunlight for at least 6 hr and then into a dark container inside the lab for up to 48 hr in which water vapor isotope ratios, temperature, and humidity were controlled. This arrangement created a step change in the forcing on the plant isotopic exchange. Leaves were sampled prior to the transfer to the dark container and 6 more times every 4 - 12 hr over the experiment. Humidity inside the container was saturated to mimic dew events in field conditions. Water from the leaf samples was extracted by a vacuum line and was analyzed for both δD and δ18O. The dataset will allow us to evaluate leaf water isotopic theories by exploring the transitions of the isotopic ratio of leaf water in response to the step change. Specifically, we are interested in whether the stomatal opening is an effective pathway for gaseous exchange in total darkness and how the transitional behaviors of the isotopic ratio of leaf water differ between the C3 and C4 photosynthesis pathways.

  13. Alternate substrates and isotope effects as a probe of the malic enzyme reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gavva, S.R.

    1988-01-01

    Dissociation constants for alternative dinucleotide substrates and competitive inhibitors suggest that the dinucleotide binding site of the Ascaris suum NAD-malic enzyme is hydrophobic in the vicinity of the nicotinamide ring. Changes in the divalent metal ion activator from Mg{sup 2+} to Mn{sup 2+} or Cd{sup 2+} results in a decrease in the dinucleotide affinity and an increase in the affinity for malate. Primary deuterium and {sup 13}C isotope effects obtained with the different metal ions suggest either a change in the transition state structure for the hydride transfer or decarboxylation steps or both. Deuterium isotope effects are finite whether reactants are maintained at saturating or limiting concentrations with all the metal ions and dinucleotide substrates used. For the native enzyme, primary deuterium isotope effects increase with a concomitant decrease in the {sup 13}C effects when NAD is replaced by an alternate dinucleotide substrate different in redox potential.

  14. Alternate substrates and isotope effects as a probe of the malic enzyme reaction

    International Nuclear Information System (INIS)

    Gavva, S.R.

    1988-01-01

    Dissociation constants for alternative dinucleotide substrates and competitive inhibitors suggest that the dinucleotide binding site of the Ascaris suum NAD-malic enzyme is hydrophobic in the vicinity of the nicotinamide ring. Changes in the divalent metal ion activator from Mg 2+ to Mn 2+ or Cd 2+ results in a decrease in the dinucleotide affinity and an increase in the affinity for malate. Primary deuterium and 13 C isotope effects obtained with the different metal ions suggest either a change in the transition state structure for the hydride transfer or decarboxylation steps or both. Deuterium isotope effects are finite whether reactants are maintained at saturating or limiting concentrations with all the metal ions and dinucleotide substrates used. For the native enzyme, primary deuterium isotope effects increase with a concomitant decrease in the 13 C effects when NAD is replaced by an alternate dinucleotide substrate different in redox potential

  15. Isotope effect in impure high T_c superconductors

    OpenAIRE

    Mierzynska, M.; Wysokinski, K. I.

    2003-01-01

    The influence of various kinds of impurities on the isotope shift exponent \\alpha of high temperature superconductors has been studied. In these materials the dopant impurities, like Sr in La_{2-x}Sr_xCuO_4, play different role and usually occupy different sites than impurities like Zn, Fe, Ni {\\it etc} intentionally introduced into the system to study its superconducting properties. In the paper the in-plane and out-of-plane impurities present in layered superconductors have been considered....

  16. Isotope effects upon translational diffusion as a probe for translation-rotation coupling in molecular liquids

    International Nuclear Information System (INIS)

    Holz, M.; Weingaertner, H.; Sacco, A.

    1990-01-01

    Mass changes of molecules caused by isotopic substitution (e.g. H-D substitution) can change the dynamic properties of a molecular liquid. Up to now, these dynamic isotope effects have been investigated only for a very small number of liquids. In the present paper we report on isotope effects upon self-diffusion coefficients, upon limiting tracer diffusion coefficients and upon viscosities of methanol, dimithylsulphoxide, dimethylformamide and nitromethane at 25deg C. It is shown that the square-root of mass dependence, which follows from a first theoretical approach, cannot predict the observed dynamic isotope effects. The experimental data correlate much better with the square root of the moments of inertia. Thus we establish a strong coupling between translational and rotational motion in these liquids. These results demonstrate that the dynamic isotope effects may serve as a sensitive probe for translation-rotation coupling in molecular liquids. The experimental finding of translation-rotation coupling is in agreement with recent computer simulations and has far consequences for the correct interpretation of liquid-state spectra as e.g. far-infrared absorption spectra. (orig.)

  17. Effect of channel coupling on the elastic scattering of lithium isotopes

    Science.gov (United States)

    Furumoto, T.; Suhara, T.; Itagaki, N.

    2018-04-01

    Herein, we investigated the channel coupling (CC) effect on the elastic scatterings of lithium (Li) isotopes (A =6 -9) for 12C and 28Si targets at E /A =50 -60 MeV. The wave functions of the Li isotopes were obtained using the stochastic multi-configuration mixing method based on the microscopic-cluster model. The proton radii of the 7Li, 8Li, and 9Li nuclei became smaller as the number of valence neutrons increased. The valence neutrons in the 8Li and 9Li nuclei exhibited a glue-like behavior, thereby attracting the α and t clusters. Based on the transition densities derived from these microscopic wave functions, the elastic-scattering cross section was calculated using a microscopic coupled-channel method with a complex G -matrix interaction. The existing experimental data for the elastic scatterings of the Li isotopes and 10Be nuclei were well reproduced. The Li isotope elastic cross sections were demonstrated for the 12C and 28Si targets at E /A =53 MeV. The glue-like effect of the valence neutrons on the Li isotope was clearly demonstrated by the CC effect on elastic scattering. Finally, we realize that the valence neutrons stabilized the bindings of the core parts and the CC effect related to core excitation was indeed reduced.

  18. Comparison of acetate turnover in methanogenic and sulfate- reducing sediments by radiolabeling and stable isotope labeling and by use of specific inhibitors: Evidence for isotopic exchange

    NARCIS (Netherlands)

    De Graaf, W.; Wellsbury, P.; Parkes, R.J.; Cappenberg, T.E.

    1996-01-01

    Acetate turnover in the methanogenic freshwater anoxic sediments of Lake Vechten, The Netherlands, and in anoxic sediments from the Tamar Estuary, United Kingdom, and the Grosser Jasmunder Bodden, Germany, the latter two dominated by sulfate reduction, was determined, Stable isotopes and

  19. Magnesium Isotopic Evidence for Ancient Subducted Oceanic Crust in LOMU-Like Potassium-Rich Volcanic Rocks

    Science.gov (United States)

    Sun, Yang; Teng, Fang-Zhen; Ying, Ji-Feng; Su, Ben-Xun; Hu, Yan; Fan, Qi-Cheng; Zhou, Xin-Hua

    2017-10-01

    To evaluate the role of subducted oceanic crust in the genesis of potassium-rich magmas, we report high-precision Mg isotopic data for a set of Cenozoic volcanic rocks from Northeast China. These rocks overall are lighter in Mg isotopic composition than the normal mantle and display considerable Mg isotopic variations, with δ26Mg ranging from -0.61 to -0.23. The covariation of δ26Mg with TiO2 in these rocks suggests that their light Mg isotopic compositions were derived from recycled oceanic crust in the form of carbonated eclogite in the source region. The strong correlations between δ26Mg and (Gd/Yb)N ratio as well as Sr-Pb isotopes further indicate a multicomponent and multistage origin of these rocks. Magnesium isotopes may thus be used as a novel tracer of recycled oceanic crust in the source region of mantle-derived magmas.

  20. Re - Os isotopic constraints on the origin of volcanic rocks, Gorgona Island, Colombia: Os isotopic evidence for ancient heterogeneities in the mantle

    Science.gov (United States)

    Walker, R.J.; Echeverria, L.M.; Shirey, S.B.; Horan, M.F.

    1991-01-01

    The Re - Os isotopic systematics of komatiites and spatially associated basalts from Gorgona Island, Colombia, indicate that they were produced at 155??43 Ma. Subsequent episodes of volcanism produced basalts at 88.1??3.8 Ma and picritic and basaltic lavas at ca. 58 Ma. The age for the ultramafic rocks is important because it coincides with the late-Jurassic, early-Cretaceous disassembly of Pangea, when the North- and South-American plates began to pull apart. Deep-seated mantle upwelling possibly precipitated the break-up of these continental plates and caused a tear in the subducting slab west of Gorgona, providing a rare, late-Phanerozoic conduit for the komatiitic melts. Mantle sources for the komatiites were heterogeneous with respect to Os and Pb isotopic compositions, but had homogeneous Nd isotopic compositions (??Nd+9??1). Initial 187Os/186Os normalized to carbonaceous chondrites at 155 Ma (??Os) ranged from 0 to +22, and model-initial ?? values ranged from 8.17 to 8.39. The excess radiogenic Os, compared with an assumed bulk-mantle evolution similar to carbonaceous chondrites, was likely produced in portions of the mantle with long-term elevated Re concentrations. The Os, Pb and Nd isotopic compositions, together with major-element constraints, suggest that the sources of the komatiites were enriched more than 1 Ga ago by low (Os isotope system may be a highly sensitive indicator of the presence of ancient subducted oceanic crust in mantle-source regions. ?? 1991 Springer-Verlag.

  1. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    -0' is also different, yielding entropy changes of -57 J K-1 mol-l in water and -84 J K-1 mol(-1) in deuterium oxide. The driving force difference of 10 mV is in keeping with the kinetic isotope effect, but the contribution to DeltaS(double dagger) from the temperature dependence of E-0' is positive......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...... entropy difference and to compensate for the different temperature dependencies of E-0'. Thus, differences in driving force and thermal expansion appear as the most straightforward rationale for the observed isotope effect....

  2. 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.)

  3. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    Science.gov (United States)

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  4. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream

    Science.gov (United States)

    Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-01-01

    ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying

  5. Isotopic evidence for two neoproterozoic high-grade metamorphic events in the Brazilia belt

    International Nuclear Information System (INIS)

    Pimentel, Marcio Martins; Fuck, Reinhardt Adolfo; Piuzanna, Danielle; Moraes, Renato de; Gioia, Simone Maria C.L

    2001-01-01

    The Brasilia Belt is part of a Brasiliano/Pan African orogen developed between the Amazon and Sao Francisco cratons. The stabilization of the belt occurred after the last metamorphic event at ca. 620 Ma. There has been increasing geochronological evidence, however, for an older Neoproterozoic metamorphic event at ca. 780 Ma, observed mainly in high grade rocks of three large mafic-ultramafic complexes in the northern part of the belt. In this study we present: (i) new U-Pb and Sm-Nd geochronological data, (ii) a review of the existing metamorphic ages in the Brasilia Belt, and (iii) a discussion on the tectonic model to explain the two Neoproterozoic metamorphic ages (au)

  6. Carbon isotopic evidence for the associations of decreasing atmospheric CO2 level with the Frasnian-Famennian mass extinction

    Science.gov (United States)

    Xu, Bing; Gu, Zhaoyan; Wang, Chengyuan; Hao, Qingzhen; Han, Jingtai; Liu, Qiang; Wang, Luo; Lu, Yanwu

    2012-03-01

    A perturbation of the global carbon cycle has often been used for interpreting the Frasnian-Famennian (F-F) mass extinction. However, the changes of atmospheric CO2 level (pCO2) during this interval are much debatable. To illustrate the carbon cycle during F-F transition, paired inorganic (δ13Ccarb) and organic (δ13Corg) carbon isotope analyses were carried out on two late Devonian carbonate sequences (Dongcun and Yangdi) from south China. The larger amplitude shift of δ13Corg compared to δ13Ccarb and its resultant Δ13C (Δ13C = δ13Ccarb - δ13Corg) decrease indicate decreased atmospheric CO2level around the F-F boundary. The onset ofpCO2 level decrease predates that of marine regressions, which coincide with the beginning of conodont extinctions, suggesting that temperature decrease induced by decreased greenhouse effect of atmospheric CO2might have contributed to the F-F mass extinction.

  7. Boron isotope evidence for the involvement of non-marine evaporites in the origin of the Broken Hill ore deposits

    Science.gov (United States)

    Slack, J.F.; Palmer, M.R.; Stevens, B.P.J.

    1989-01-01

    IDENTIFYING the palaeogeographic setting and mode of origin of stratabound ore deposits can be difficult in high-grade metamorphic terranes, where the effects of metamorphism may obscure the nature of the protoliths. Here we report boron isotope data for tourmalines from the early Proterozoic Broken Hill block, in Australia, which hosts giant lead-zinc-silver sulphide deposits. With one exception the 11B/10B ratios are lower than those for all other tourmalines from massive sulphide deposits and tour-malinites elsewhere in the world. We propose that these low ratios reflect leaching of boron from non-marine evaporitic borates by convecting hydrothermal fluids associated with early Proterozoic continental rifting. A possible modern analogue is the Salton Sea geothermal field in California. ?? 1989 Nature Publishing Group.

  8. A multielement isotopic study of refractory FUN and F CAIs: Mass-dependent and mass-independent isotope effects

    Science.gov (United States)

    Kööp, Levke; Nakashima, Daisuke; Heck, Philipp R.; Kita, Noriko T.; Tenner, Travis J.; Krot, Alexander N.; Nagashima, Kazuhide; Park, Changkun; Davis, Andrew M.

    2018-01-01

    Calcium-aluminum-rich inclusions (CAIs) are the oldest dated objects that formed inside the Solar System. Among these are rare, enigmatic objects with large mass-dependent fractionation effects (F CAIs), which sometimes also have large nucleosynthetic anomalies and a low initial abundance of the short-lived radionuclide 26Al (FUN CAIs). We have studied seven refractory hibonite-rich CAIs and one grossite-rich CAI from the Murchison (CM2) meteorite for their oxygen, calcium, and titanium isotopic compositions. The 26Al-26Mg system was also studied in seven of these CAIs. We found mass-dependent heavy isotope enrichment in all measured elements, but never simultaneously in the same CAI. The data are hard to reconcile with a single-stage melt evaporation origin and may require reintroduction or reequilibration for magnesium, oxygen and titanium after evaporation for some of the studied CAIs. The initial 26Al/27Al ratios inferred from model isochrons span a range from <1 × 10-6 to canonical (∼5 × 10-5). The CAIs show a mutual exclusivity relationship between inferred incorporation of live 26Al and the presence of resolvable anomalies in 48Ca and 50Ti. Furthermore, a relationship exists between 26Al incorporation and Δ17O in the hibonite-rich CAIs (i.e., 26Al-free CAIs have resolved variations in Δ17O, while CAIs with resolved 26Mg excesses have Δ17O values close to -23‰). Only the grossite-rich CAI has a relatively enhanced Δ17O value (∼-17‰) in spite of a near-canonical 26Al/27Al. We interpret these data as indicating that fractionated hibonite-rich CAIs formed over an extended time period and sampled multiple stages in the isotopic evolution of the solar nebula, including: (1) an 26Al-poor nebula with large positive and negative anomalies in 48Ca and 50Ti and variable Δ17O; (2) a stage of 26Al-admixture, during which anomalies in 48Ca and 50Ti had been largely diluted and a Δ17O value of ∼-23‰ had been achieved in the CAI formation region; and (3

  9. The isotope effect in the thermodynamic parameters of polymerization of styrene

    International Nuclear Information System (INIS)

    Lebedev, B.V.; Kirillin, A.I.; Kozyreva, N.M.; Lebedev, N.K.; Smirnova, N.N.

    1985-01-01

    This paper studies the effect of substitution of hydrogen by deuterium on the thermodynamic criteria of polymerization processes. The isotope effects in the enthalpy, entropy, and Gibbs energy of the polymerization of styrene are studied by the methods of adiabatic and isothermal calorimetry. The heat capacity of polystyrenes and polydeuterostyrenes are shown

  10. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...

  11. Solvent isotope effects on the rates of alkylation of thiolamine models of papain

    International Nuclear Information System (INIS)

    Wandinger, A.; Creighton, D.J.

    1980-01-01

    As a test of whether it is chemically reasonable to attribute any or all of the observed kinetic solvent deuterium isotope effects reported on papain to the fundamental properties of the tautomerization equilibrium, the magnitudes of the solvent deuterium isotope effects on the rates of alkylation of the tautomeric forms of cysteine and β-mercaptoethylamine were determined for bromo- and chloroacetate, bromo- and chloroacetamide, as well as for methylbromoacetate. These thiolamines are viewed as elementary chemical models of the sulfhydryl group tautomerization equilibrium envisioned in the active site of papain. (Auth.)

  12. The kinetic deuterium isotope effect in the thermal dehydration of boric acid

    International Nuclear Information System (INIS)

    Tanaka, H.; Ohshima, S.; Ichiba, S.; Negita, H.

    1981-01-01

    The kinetic deuterium isotope effect in the thermal dehydration process from H 3 BO 3 to HBO 2 (III) was determined using simultaneous TG and DSC. The rate constant ratio of H 3 BO 3 to D 3 BO 3 obtained by the analysis of isothermal TG and DSC curves was found to be smaller than unity. Both activation energy, E, and frequency factor, A, for the dehydration of H 3 BO 3 proved to be larger than those of D 3 BO 3 , using non-isothermal TG and DSC. The origin of the deuterium kinetic isotope effect in the thermal dehydration of boric acid is also briefly discussed. (orig.)

  13. Structural, physiological, and stable carbon isotopic evidence that the enigmatic Paleozoic fossil Prototaxites formed from rolled liverwort mats.

    Science.gov (United States)

    Graham, Linda E; Cook, Martha E; Hanson, David T; Pigg, Kathleen B; Graham, James M

    2010-02-01

    New structural, nutritional, and stable carbon isotope data may resolve a long-standing mystery-the biological affinities of the fossil Prototaxites, the largest organism on land during the Late Silurian to Late Devonian (420-370 Ma). The tree trunk-shaped specimens, of varying dimensions but consistent tubular anatomy, first formed prior to vascular plant dominance. Hence, Prototaxites has been proposed to represent giant algae, fungi, or lichens, despite incompatible biochemical and anatomical observations. Our comparative analyses instead indicate that Prototaxites formed from partially degraded, wind-, gravity-, or water-rolled mats of mixotrophic liverworts having fungal and cyanobacterial associates, much like the modern liverwort genus Marchantia. We propose that the fossil body is largely derived from abundant, highly degradation-resistant, tubular rhizoids of marchantioid liverworts, intermixed with tubular microbial elements. Our concept explains previously puzzling fossil features and is consistent with evidence for liverworts and microbial associates in Ordovician-Devonian deposits, extensive ancient and modern marchantioid mats, and modern associations of liverworts with cyanobacteria and diverse types of fungi. Our interpretation indicates that liverworts were important components of Devonian ecosystems, that some macrofossils and microfossils previously attributed to "nematophytes" actually represent remains of ancient liverworts, and that mixotrophy and microbial associations were features of early land plants.

  14. Stable Isotope Evidence for Late Medieval (14th–15th C) Origins of the Eastern Baltic Cod (Gadus morhua) Fishery

    Science.gov (United States)

    Orton, David C.; Makowiecki, Daniel; de Roo, Tessa; Johnstone, Cluny; Harland, Jennifer; Jonsson, Leif; Heinrich, Dirk; Enghoff, Inge Bødker; Lõugas, Lembi; Van Neer, Wim; Ervynck, Anton; Hufthammer, Anne Karin; Amundsen, Colin; Jones, Andrew K. G.; Locker, Alison; Hamilton-Dyer, Sheila; Pope, Peter; MacKenzie, Brian R.; Richards, Michael; O'Connell, Tamsin C.; Barrett, James H.

    2011-01-01

    Although recent historical ecology studies have extended quantitative knowledge of eastern Baltic cod (Gadus morhua) exploitation back as far as the 16th century, the historical origin of the modern fishery remains obscure. Widespread archaeological evidence for cod consumption around the eastern Baltic littoral emerges around the 13th century, three centuries before systematic documentation, but it is not clear whether this represents (1) development of a substantial eastern Baltic cod fishery, or (2) large-scale importation of preserved cod from elsewhere. To distinguish between these hypotheses we use stable carbon and nitrogen isotope analysis to determine likely catch regions of 74 cod vertebrae and cleithra from 19 Baltic archaeological sites dated from the 8th to the 16th centuries. δ13C and δ15N signatures for six possible catch regions were established using a larger sample of archaeological cod cranial bones (n = 249). The data strongly support the second hypothesis, revealing widespread importation of cod during the 13th to 14th centuries, most of it probably from Arctic Norway. By the 15th century, however, eastern Baltic cod dominate within our sample, indicating the development of a substantial late medieval fishery. Potential human impact on cod stocks in the eastern Baltic must thus be taken into account for at least the last 600 years. PMID:22110675

  15. Correlation of the vapor pressure isotope effect with molecular force fields in the liquid state

    Energy Technology Data Exchange (ETDEWEB)

    Pollin, J.S.; Ishida, T.

    1976-07-01

    The present work is concerned with the development and application of a new model for condensed phase interactions with which the vapor pressure isotope effect (vpie) may be related to molecular forces and structure. The model considers the condensed phase as being represented by a cluster of regularly arranged molecules consisting of a central molecule and a variable number of molecules in the first coordination shell. The methods of normal coordinate analysis are used to determine the modes of vibration of the condensed phase cluster from which, in turn, the isotopic reduced partition function can be calculated. Using the medium cluster model, the observed vpie for a series of methane isotopes has been successfully reproduced with better agreement with experiment than has been possible using the simple cell model. We conclude, however, that insofar as the medium cluster model provides a reasonable picture of the liquid state, the vpie is not sufficiently sensitive to molecular orientation to permit an experimental determination of intermolecular configuration in the condensed phase through measurement of isotopic pressure ratios. The virtual independence of vapor pressure isotope effects on molecular orientation at large cluster sizes is a demonstration of the general acceptability of the cell model assumptions for vpie calculations.

  16. Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

    Science.gov (United States)

    Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

    2006-12-15

    The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

  17. Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

    International Nuclear Information System (INIS)

    Nishikawa, M.; Baba, A.; Kawamura, Y.; Nishi, M.

    1998-01-01

    Though lithium ceramic materials such as Li 2 O, LiAlO 2 , Li 2 ZrO 3 , Li 2 TiO 3 and Li 4 SiO 4 are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H 2 and D 2 O or that between D 2 and H 2 O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li 2 ZrO 3 blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

  18. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    Science.gov (United States)

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H.

    2017-02-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  19. Evidence for substantial forestry canopy processing of nitrogen deposition using isotopic tracer experiments in low deposition conditions

    Science.gov (United States)

    Ferraretto, Daniele; Heal, Kate

    2017-04-01

    Temperate forest ecosystems are significant sinks for nitrogen deposition (Ndep) yielding benefits such as protection of waterbodies from eutrophication and enhanced sequestration of atmospheric CO2. Previous studies have shown evidence of biological nitrification and Ndep processing and retention in forest canopies. However, this was reported only at sites with high environmental or experimentally enhanced rates of Ndep (˜18 kg N ha-1 y-1) and has not yet been demonstrated in low Ndep environments. We have used bulk field hydrochemical measurements and labelled isotopic experiments to assess canopy processing in a lower Ndep environment (˜7 kg N ha-1 year-1) at a Sitka spruce plantation in Perthshire, Scotland, representing the dominant tree species (24%) in woodlands in Great Britain. Analysis of 4.5 years of measured N fluxes in rainfall (RF) and fogwater onto the canopy and throughfall (TF) and stemflow (SF) below the canopy suggests strong transformation and uptake of Ndep in the forest canopy. Annual canopy Ndep uptake was ˜4.7 kg N ha-1 year-1, representing 60-76% of annual Ndep. To validate these plot-scale results and track N uptake within the forest canopy in different seasons, double 15N-labelled NH4NO3 (98%) solution was sprayed in summer and winter onto the canopy of three trees at the measurement site. RF, TF and SF samples have been collected and analysed for 15NH4 and 15NO3. Comparing the amount of labelled N recovered under the sample trees with the measured δ15N signal is expected to provide further evidence of the role of forest canopies in actively processing and retaining atmospheric N deposition.

  20. Isotopic effects in the neon fixed point: uncertainty of the calibration data correction

    Science.gov (United States)

    Steur, Peter P. M.; Pavese, Franco; Fellmuth, Bernd; Hermier, Yves; Hill, Kenneth D.; Seog Kim, Jin; Lipinski, Leszek; Nagao, Keisuke; Nakano, Tohru; Peruzzi, Andrea; Sparasci, Fernando; Szmyrka-Grzebyk, Anna; Tamura, Osamu; Tew, Weston L.; Valkiers, Staf; van Geel, Jan

    2015-02-01

    The neon triple point is one of the defining fixed points of the International Temperature Scale of 1990 (ITS-90). Although recognizing that natural neon is a mixture of isotopes, the ITS-90 definition only states that the neon should be of ‘natural isotopic composition’, without any further requirements. A preliminary study in 2005 indicated that most of the observed variability in the realized neon triple point temperatures within a range of about 0.5 mK can be attributed to the variability in isotopic composition among different samples of ‘natural’ neon. Based on the results of an International Project (EUROMET Project No. 770), the Consultative Committee for Thermometry decided to improve the realization of the neon fixed point by assigning the ITS-90 temperature value 24.5561 K to neon with the isotopic composition recommended by IUPAC, accompanied by a quadratic equation to take the deviations from the reference composition into account. In this paper, the uncertainties of the equation are discussed and an uncertainty budget is presented. The resulting standard uncertainty due to the isotopic effect (k = 1) after correction of the calibration data is reduced to (4 to 40) μK when using neon of ‘natural’ isotopic composition or to 30 μK when using 20Ne. For comparison, an uncertainty component of 0.15 mK should be included in the uncertainty budget for the neon triple point if the isotopic composition is unknown, i.e. whenever the correction cannot be applied.

  1. Hydrodynamic and Environmental Controls on the Nitrogen Isotope Effect of Benthic N2 Production

    Science.gov (United States)

    Rooze, J.; Meile, C. D.

    2016-02-01

    Isotopic signatures of nitrogen (N) pools, together with knowledge on fractionation during the conversion between different forms of N, can be used to constrain marine N budgets. However, the reported extent of N isotope fractionation during benthic N2 production has differed substantially between studies, leading to uncertainty in the estimate of the global benthic N2 production rate. To assess the range and identify mechanisms underlying such observations, we developed a reactive transport model and ran simulations evaluating the impact of nitrification, denitrification, and anaerobic ammonium oxidation on the isotopic composition of in-situ N/2 production. Different hydrodynamic regimes were taken into account, including advective flow induced by bioirrigation and purely diffusive transport. The effects of the benthic mineralization rate and the composition of the overlying water were also quantified. The benthic redox conditions were found to control the N isotope effect, which under reducing conditions is driven by fractionation during nitrification and anaerobic ammonium oxidation and under oxidizing conditions by fractionation during denitrification. The mineralization rate, the bioirrigation intensity, and chemical composition of the overlying water affect the benthic redox zonation and therefore also the benthic N isotope effect. With increasing water-depth the mineralization rate and the advective nitrate supply to the sediment both decrease, constraining most benthic N cycling to the continental shelf. Simulations that reproduce observed trends of sediment O2 uptake and N2 fluxes with water depth, combined with ocean bathymetry yield an average benthic N isotope effect of -3‰, in line with independent estimates from global circulation models coupled to N cycle models (Somes et al., 2013. Biogeosciences 10, 5889-5910).

  2. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    Science.gov (United States)

    Green, C.T.; Böhlke, J.K.; Bekins, B.A.; Phillips, S.P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field-scale (apparent) estimated reaction rates and isotopic fractionations and local-scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O 2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample-based estimates of "apparent" parameters with "true" (intrinsic) values. For this aquifer, non-Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2 threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport. ?? 2010 by the American Geophysical Union.

  3. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    Science.gov (United States)

    Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

  4. Ab initio calculation of the Zn isotope effect in phosphates, citrates, and malates and applications to plants and soil.

    Science.gov (United States)

    Fujii, Toshiyuki; Albarède, Francis

    2012-01-01

    Stable Zn isotopes are fractionated in roots and leaves of plants. Analyses demonstrate that the heavy Zn isotopes are enriched in the root system of plants with respect to shoots and leaves as well as the host soil, but the fractionation mechanisms remain unclear. Here we show that the origin of this isotope fractionation is due to a chemical isotope effect upon complexation by Zn malates and citrates in the aerial parts and by phosphates in the roots. We calculated the Zn isotope effect in aqueous citrates, malates, and phosphates by ab initio methods. For pHphosphates, with respect to leaves, which concentrate malates and citrates, by about one permil. It is proposed that Zn isotope fractionation represents a useful tracer of Zn availability and mobility in soils.

  5. Variability of pesticides and nitrates concentrations along a river transect: chemical and isotopic evidence of groundwater - surface water interconnections

    Science.gov (United States)

    Baran, Nicole; Petelet-Giraud, Emmanuelle; Saplairoles, Maritxu

    2015-04-01

    concentration. Finally, downstream the quantified pesticides were different from those observed in the upper part of the Crieu but similar to those observed in groundwater. Sr isotopes together with major elements and Sr concentrations allow to identify 3 distinct end-members to explain the river quality evolution : 1) surface water, 2) groundwater and 3) sub-surface water. On this basis, we first demonstrate that the contribution of the different end-members to the river flow is highly variable from upstream to downstream. Secondly, we evidence water exchanges between the river and the groundwater compartment and vice-versa. The combination of the isotopic and geochemical approaches was essential to understand the complex relations and exchanges between surface and ground-waters occurring in few kilometers along the Crieu River. This understanding allows the comprehension of spatial variability of surface water quality. This is of primary importance when to help water managers to select relevant sampling points to be monitored in the framework of the WFD. Amalric L., et al. (2013). International Journal of Environmental Analytical Chemistry, 93: 1660-1675 Loos R. et al. (2010). Water Research, 44: 4115-4126 Stuart M. et al. (2012). Science of the Total Environment, 416: 1-21.

  6. Unusual Atmospheric Processes: Implications for the Unusual Isotope Effect in Precipitation

    Science.gov (United States)

    Hurst, S.; Krishnamurthy, R. V.

    2016-12-01

    Several samples associated in particular with thunderstorms collected from Kalamazoo, Michigan reveal oxygen and hydrogen isotope ratios that are not compatible with known thermodynamic fractionation or the so-called Raleigh Distillation Effect. Data gathered from April 2014 to February 2016 can be separated into two categories: (1) samples with expected isotopic values based on previous work, (2) samples with unusually high δ18O and δ2H values. Values as high as 42‰ and 25‰ for δ2H and δ18O respectively are obtained. Recent studies suggest that precipitation produced by deep convection can produce moderately enriched oxygen isotopic values, although no hydrogen values for those precipitations are available. Moreover, no values have been recorded that are as high as some of those presented here. The unusual isotope values cannot be attributed to air mass contributions. It is argued that changes in atmospheric chemistry, most likely induced by lightning associated with thunderstorms are responsible. This is likely since temperatures associated with lightning can reach 40000°K. Several studies have indicated that lightning can significantly impact atmospheric chemistry producing, among other species, ozone and NOx. Atmospheric ozone has enriched isotopic values and likely contributes to enriched Oxygen-18 seen in precipitation. An explanation for enrichment in hydrogen is somewhat elusive, but a likely candidate is ion molecular reactions produced by extremely high temperatures in the corona of lightning.

  7. Isotopic and spin-nuclear effects in solid hydrogens (Review Article)

    Science.gov (United States)

    Freiman, Yuri A.; Crespo, Yanier

    2017-12-01

    The multiple isotopic family of hydrogens (H2, HD, D2, HT, DT, T2) due to large differences in the de Boer quantum parameter and inertia moments displays a diversity of pronounced quantum isotopic solid-state effects. The homonuclear members of this family (H2, D2, T2) due to the permutation symmetry are subjects of the constraints of quantum mechanics which link the possible rotational states of these molecules to their total nuclear spin giving rise to the existence of two spin-nuclear modifications, ortho- and parahydrogens, possessing substantially different properties. Consequently, hydrogen solids present an unique opportunity for studying both isotope and spin-nuclear effects. The rotational spectra of heteronuclear hydrogens (HD, HT, DT) are free from limitations imposed by the permutation symmetry. As a result, the ground state of these species in solid state is virtually degenerate. The most dramatic consequence of this fact is an effect similar to the Pomeranchuk effect in 3He which in the case of the solid heteronuclear hydrogens manifests itself as the reentrant broken symmetry phase transitions. In this review article we discuss thermodynamic and kinetic effects pertaining to different isotopic and spin-nuclear species, as well as problems that still remain to be solved.

  8. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear......; at 300 K, the isotopic fractionation was found to be (34)e = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)e in OCS photolysis and OH oxidation are not larger than 10‰, indicating that...

  9. Note on isotopic effects in range calculations of high-energy ion beams

    International Nuclear Information System (INIS)

    Dominguez-Vazquez, Javier; Perez-Martin, A.M.C.; Jimenez-Rodriguez, J.J.; Konoplev, Vladimir; Gras-Marti, Albert; Castella-Mayor, Javier

    1995-01-01

    A simple analytical model that allows the calculation of the percent-level differences of the average ranges of isotopic ion beams slowing down in solid targets is extended to energies in the MeV region and to investigate isotopic effects due to small variations in the mass of the target species. The various contributions to the range in terms of ion stopping, both nuclear and electronic, and angular scattering, can be investigated separately. The model agrees with available experimental data, and predictions are made for a range of cases of interest. (orig.)

  10. Study on the Effect of the Separating Unit Optimization on the Economy of Stable Isotope Separation

    Directory of Open Access Journals (Sweden)

    YANG Kun

    2015-01-01

    Full Text Available An economic criterion called as yearly net profit of single separating unit (YNPSSU was presented to evaluate the influence of structure optimization on the economy. Using YNPSSU as a criterion, economic analysis was carried out for the structure optimization of separating unit in the case of separating SiF4 to obtain the 28Si and 29Si isotope. YNPSSU was calculated and compared with that before optimization. The results showed that YNPSSU was increased by 12.3% by the structure optimization. Therefore, the structure optimization could increase the economy of the stable isotope separation effectively.

  11. An experimental investigation of the isotope effect in the CVD growth of diamonds

    International Nuclear Information System (INIS)

    Vakil, H.B.; Banholzer, W.F.; Kehl, R.J.; Spiro, C.L.

    1989-01-01

    An experimental investigation of the effect of isotopic substitution of hydrogen by deuterium was carried out for the chemical vapor deposition (CVD) of diamond films to determine whether the rate determining step involves a C-H or a C-C bond. Results show that if such a comparison is carried out in a proper manner the growth rate with deuterium is slower by the expected isotopic factor of the square root of 2, indicating that most likely a C-H bond is involved in the rate limiting step. Additionally, it is found that the kinetics of the atomic species generation were equally affected by the isotopic switch, strongly suggesting that the rate limiting step for that process involves the metal-H bond

  12. Pedogenic carbonate stable isotopic evidence for wooded habitat preference of early Pleistocene tool makers in the Turkana Basin.

    Science.gov (United States)

    Quinn, Rhonda L; Lepre, Christopher J; Feibel, Craig S; Wright, James D; Mortlock, Richard A; Harmand, Sonia; Brugal, Jean-Philip; Roche, Hélène

    2013-07-01

    The origin and evolution of early Pleistocene hominin lithic technologies in Africa occurred within the context of savanna grassland ecosystems. The Nachukui Formation of the Turkana Basin in northern Kenya, containing Oldowan and Acheulean tool assemblages and fossil evidence for early members of Homo and Paranthropus, provides an extensive spatial and temporal paleosol record of early Pleistocene savanna flora. Here we present new carbon isotopic (δ(13)CVPDB) values of pedogenic carbonates (68 nodules, 193 analyses) from the Nachukui Formation in order to characterize past vegetation structure and change through time. We compared three members (Kalochoro, Kaitio, and Natoo) at five locations spanning 2.4-1.4Ma and sampled in proximity to hominin archaeological and paleontological sites. Our results indicate diverse habitats showing a mosaic pattern of vegetation cover at each location yet demonstrate grassland expansion through time influenced by paleogeography. Kalochoro floodplains occurred adjacent to large river systems, and paleosols show evidence of C3 woodlands averaging 46-50% woody cover. Kaitio habitats were located along smaller rivers and lake margins. Paleosols yielded evidence for reduced portions of woody vegetation averaging 34-37% woody cover. Natoo environments had the highest percentage of grasslands averaging 21% woody cover near a diminishing Lake Turkana precursor. We also compared paleosol δ(13)CVPDB values of lithic archaeological sites with paleosol δ(13)CVPDB values of all environments available to hominins at 2.4-1.4Ma in the Nachukui and Koobi Fora Formations. Grassy environments became more widespread during this interval; woody canopy cover mean percentages steadily decreased by 12%. However, significantly more wooded savanna habitats were present in the vicinity of lithic archaeological sites and did not mirror the basin-wide trend of grassland spread. Hominin lithic archaeological sites consistently demonstrated woody cover

  13. Carbon-13 kinetic isotope effects in the decarbonylations of lactic acid containing 13C at the natural abundance level

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.

    1992-01-01

    The 13 C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20-80 deg C. The 13 C (1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40 deg C. Below this temperature the 13 C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found in the decarbonylation of lactic [1- 14 C] acid. The experimental values of k (12C) /k (13C) ratios of isotopic rate constants for 12 C and 13 C are close to, but slightly higher than theoretical 13 C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C (1) -OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H 2 O)/(H 2 SO 4 ) ratio caused the increase of the 13 C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5 deg C to 1.0536±0.0008 (at 80.6 deg C). A discussion of the abnormally high temperature dependence of 14 C and 13 C isotope fractionation in this reaction and the discussion of the problem of relative 14 C/ 13 C kinetic isotope effects is given. (author) 18 refs.; 2 tabs

  14. Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

    International Nuclear Information System (INIS)

    Markham, G.D.; Parkin, D.W.; Schramm, V.L.

    1986-01-01

    S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

  15. Fine print in isotope effects: the glucose anomeric equilibrium and binding of glucose to human brain hexokinase

    International Nuclear Information System (INIS)

    Lewis, B.E; Schramm, V.L.

    2002-01-01

    Binding isotope effects are a sensitive measure of changes in molecular vibrational character that occur during ligand-receptor binding. In this study, we have measured isotope effects on the binding of glucose to human brain hexokinase using the ultrafiltration method, with the following results: 0.991±0.001, 0.908±0.003, 1.010±0.001, 0.974±0.002, 1.022±0.002 for [ 14 C]-glucose mixed with [1- 3 H]-, [2- 3 H]-, [3- 3 H]-, [5- 3 H]-, [6,6- 3 H]-glucose, respectively. Comparing the observed data with isotope effects on the anomeric equilibrium in glucose reported previously proves the existence of binding isotope effects in this system. Preliminary computational results are presented to explain the observed binding isotope effects in terms of hydrogen bond patterns and molecular crowding found in the binary complex of sugar and enzyme. (author)

  16. Basic study on isotope separation using light induced drift effects (Progress report)

    Energy Technology Data Exchange (ETDEWEB)

    Suto, Osamu; Yamaguchi, Hiromi; Suzuki, M. [Japan Nuclear Cycle Development Inst., Tokai, Ibaraki (Japan). Tokai Works; Ishii, K.

    1999-03-01

    As a preliminary research on {sup 15}N-isotope separation on the basis of light induced drift (LID) effects in NH{sub 3}, the authors have confirmed the feasibility on {sup 13}C-isotope separation using LID effects in CH{sub 3}F for which all the necessary spectroscopic data are available and found that: (1) Concentration difference at the entrance and at the exit end of the drift tube {delta}n{sub a} (number/cm{sup 3}) was proportional to the energy density absorbed ({delta}W/cm{sup 2}), indicating the validity of theoretical LID equation. (2) Pressure dependence of {delta}n{sub a}/{delta}S was maximum at ca. 0.5 Torr. Lower {delta}n{sub a}/{delta}S values are due to power saturation effects at low pressures and due to absorption line broadening at high pressures. (3) Maximum isotopic selectivity was obtained at 0.5 Torr and to be 1.18. (4) Time needed for {delta}n{sub a} to attain the equilibrium increased with increasing pressure. They concluded that the possibility of {sup 15}N isotope separation using NH{sub 3}-LID effect was in principle confirmed. (S. Ohno)

  17. A new cascade method for studying isotope effect in chemical exchange system without valance change

    International Nuclear Information System (INIS)

    Wen Xiaoning; Luo Wenzong

    1987-01-01

    A new cascade method for studying isotope effect in chemical exchange system without valance change is developed and described. This method is simple to use and consumes less extractant as compared with the commonly used Woodward method. It is also convenient for unstable systems

  18. Neutron skin effect of some Mo isotopes in pre-equilibrium reactions

    Indian Academy of Sciences (India)

    The neutron skin effect has been investigated for even isotopes of molybdenum at 25.6 MeV 94−100Mo(, ) reaction using the geometry-dependent hybrid model of pre-equilibrium nuclear reactions. Here the initial neutron/proton exciton numbers were calculated from the neutron/proton densities obtained from an ...

  19. Kinetic Isotope Effects (KIE) and Density Functional Theory (DFT): A Match Made in Heaven?

    DEFF Research Database (Denmark)

    Christensen, Niels Johan; Fristrup, Peter

    2015-01-01

    Determination of experimental kinetic isotope effects (KIE) is one of the most useful tools for the exploration of reaction mechanisms in organometallic chemistry. The approach has been further strengthened during the last decade with advances in modern computational chemistry. This allows for th...

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

    DEFF Research Database (Denmark)

    Hansen, Poul Erik

    2015-01-01

    The paper deals with the use of isotope effects on chemical shifts in characterizing intramolecular hydrogen bonds. Both so-called resonance-assisted (RAHB) and non-RAHB systems are treated. The importance of RAHB will be discussed. Another very important issue is the borderline between “static” ...

  1. Stable isotope enrichment in laboratory ant colonies: effects of colony age, metamorphosis, diet, and fat storage

    Science.gov (United States)

    Ecologists use stable isotopes to infer diets and trophic levels of animals in food webs, yet some assumptions underlying these inferences have not been thoroughly tested. We used laboratory-reared colonies of Solenopsis invicta Buren (Formicidae: Solenopsidini) to test the effects of metamorphosis,...

  2. Absence of an effect of freshwater input on the stable isotope and ...

    African Journals Online (AJOL)

    We investigated the potential effects of freshwater input on the diets of intertidal benthic organisms in situ on the east coast of South Africa, analysing their δ13C and δ15N stable isotope and fatty acid content. Specifically, we investigated the dietary regime of three barnacle and one mussel species in relation to their ...

  3. Kinetic mechanism and isotope effects of Pseudomonas cepacia 3-hydroxybenzoate-t-hydroxylase

    International Nuclear Information System (INIS)

    Wang, L.H.; Yu, Y.; Hamzah, R.Y.; Tu, S.C.

    1986-01-01

    The kinetic mechanism of Pseudomonas cepacia 3-hydroxybenzoate-6-hydroxylase has been delineated. Double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a constant level of oxygen and several fixed concentrations of NADH yielded a set of converging lines. Similar reciprocal plots of velocity versus NADH concentration at a constant oxygen level and several fixed m-hydroxybenzoate concentrations also showed converging lines. In contrast, double reciprocal plots of initial rate versus NADH concentration at a fixed m-hydroxybenzoate level and several oxygen concentrations showed a series of parallel lines. Parallel lines were also obtained from double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a fixed NADH level and varying oxygen concentrations. These results suggest a sequential binding of m-hydroxybenzoate and NADH by the hydroxylase. The enzyme-bound FAD is reduced and NAD is released. The reduced enzyme subsequently reacts with oxygen leading to the formation of other products. This hydroxylase exhibited a primary isotope effect of /sup D/V = 3.5 for (4R)-[4- 2 H] NADH but no isotope effect was observed with (4S)-[4- 2 H]NADH. An isotope effect of /sup T/V/K = 5.0 was also observed using (4R)-[4- 3 H]NADH. This tritium isotope effect was apparently independent of m-hydroxybenzoate concentration

  4. Phylogenetically balanced evidence for structural and carbon isotope responses in plants along elevational gradients.

    Science.gov (United States)

    Zhu, Yuan; Siegwolf, Rolf T W; Durka, Walter; Körner, Christian

    2010-04-01

    We tested three hypotheses related to the functioning of mountain plants, namely their reproductive effort, leaf surface structure and effectiveness of CO(2) assimilation, using archive material from contrasting elevations. Analysis of elevational trends is at risk of suffering from two major biases: a phylogenetic bias (i.e. an elevational change in the abundance of taxonomic groups), and covariation of different environmental drivers (e.g. water, temperature, atmospheric pressure), which do not permit a mechanistic interpretation. We solved both problems in a subcontinental survey of elevational trends in key plant traits in the European Alps and the high Arctic (northern Sweden, Svalbard), using herbarium samples of 147 species belonging to the genera Carex, Saxifraga and Potentilla. We used both species and phylogenetically independent contrasts as data points. The analysis revealed enhanced reproductive efforts at higher elevation in insect-pollinated taxa (not in wind-pollinated taxa), no increase in leaf pubescence at high elevation (as is often assumed), and a strong correlation between (13)C discrimination and elevation. Alpine taxa operate at a smaller mesophyll resistance to CO(2) uptake relative to diffusive resistance (stomata). By comparison with congeneric low altitude polar taxa (low temperature, but high atmospheric pressure), the response could be attributed to the elevational decline in atmospheric pressure rather than temperature (a mean increase in delta(13)C by 1.4 per thousand km(-1)). The signal is consistent within and across genera and within species, suggesting rapid adjustment of leaf physiology to reduced partial pressure of CO(2). These results offer answers to long-debated issues of plant responses to high elevation life conditions.

  5. Production and identification of heavy Ni isotopes: Evidence for the doubly magic nucleus 7828Ni. Short note

    International Nuclear Information System (INIS)

    Engelmann, C.; Ameil, F.; Bernas, M.; Heinz, A.; Janas, Z.; Kozhuharov, C.; Miehe, C.; Pfuetzner, M.; Roehl, C.; Stephan, C.; Tassan-Got, L.; Voss, B.

    1995-07-01

    We report the first observation of the doubly magic nucleus 78 Ni 50 and the heavy isotopes 77 Ni, 73,74,75 Co, 80 Cu. The isotopes were produced by nuclear fission in collisions of 750 A.MeV projectiles of 238 U on Be target nuclei. The fully-stripped fission products were separated in-flight by the fragment separator FRS and identified event-by-event by measuring the magnetic rigidity, the trajectory, the energy deposit, and the time of flight. Production cross-sections and fission yields for the new Ni-isotopes are given. (orig.)

  6. Effect of Calcium Oxide Microstructure on the Diffusion of Isotopes

    CERN Document Server

    Fernandes Ramos, João Pedro; Stora, T

    2012-01-01

    Calcium oxide (CaO) powder targets have been successfully used at CERN-ISOLDE to produce neutron deficient exotic argon and carbon isotopes under proton irradiation at high temperatures (>1000°C). These targets outperform the other related targets for the production of the same beams. However, they presented either slow release rates (yields) from the beginning or a rapid decrease over time. This problem was believed to come from the target microstructure degradation, justifying the material investigation. In order to do so, the synthesis, reactivity in ambient air and sintering kinetics of CaO were studied, through surface area determination by N2 adsorption, X-ray diffraction for crystalline phase identification and crystallite size determination, and scanning and transmission electron microscopy to investigate the microstructure. The synthesis studies revealed that a nanometric material is obtained from the decarbonation of CaCO3 in vacuum at temperatures higher than 550°C, which is very reactive in air....

  7. Shell effect in the mean square charge radii and magnetic moments of bismuth isotopes near N =126

    Science.gov (United States)

    Barzakh, A. E.; Fedorov, D. V.; Ivanov, V. S.; Molkanov, P. L.; Moroz, F. V.; Orlov, S. Yu.; Panteleev, V. N.; Seliverstov, M. D.; Volkov, Yu. M.

    2018-01-01

    Isotope shift relative to 209Bi and hyperfine splitting for Bi,213211 have been measured by in-source laser spectroscopy at the 306.77-nm atomic transition. The pronounced shell effect both in radii and magnetic moments in Bi isotopes at N =126 has been observed. The isotopic trend of magnetic moment for 9 /2- ground states of even-N Bi isotopes has been qualitatively explained by the change in the first-order core-polarization correction. The possible influence of the octupole degree of freedom on the magnetic moment behavior at N >126 has been discussed.

  8. Magnetic isotopic effect and mechanisms of chemical reactions. Photolysis of dimethylphenylsilyl phenyl ketone and of its carbon analog in micelles

    International Nuclear Information System (INIS)

    Step, E.N.; Tarasov, V.F.; Buchachenko, A.L.

    1986-01-01

    In the photolysis of cumyl phenyl ketone in micelles, for which photodecomposition occurs with the formation of a triplet geminal radical pair (Norrish type-I breakdown), with high efficiency the separation of carbon isotopes, induced by the magnetic isotopic effect, occurs for the original ketone. The isotopic composition of dimethylphenylsilyl phenyl ketone, either with respect to carbon or with respect to silicon, does not change in photolysis, i.e., in the primary act of the photolysis the separation of isotopes does not occur. It follows that the primary act of the photolysis of the ketone is not the formation of a radical pair, but is probably isomerization into a carbene

  9. Does Size Really Matter? The Steric Isotope Effect in a Supramolecular Host?Guest Exchange Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2010-01-29

    Isotope effects (IEs), which arise from differences in zero point energies (ZPEs) between a parent and isotopically substituted bond, have been used extensively by chemists to probe molecular interactions and reactivity. Due to the anharmonicity of the C-H/D vibrational potential energy function and the lower ZPE of a C-D bond, the average C-D bond length is typically {approx}0.005 {angstrom} shorter than an equivalent C-H bond. It is this difference in size that is often invoked to explain the observation of secondary, inverse kinetic isotope effects (KIEs) in chemical processes which proceed through a sterically strained transition state. This so-called 'steric isotope effect' (SIE) has been observed in processes such as the racemization of ortho-substituted biphenyls[6] and phenanthrenes, ring flipping of cyclophanes, and more recently in the deslipping of rotaxanes, where substitution of the sterically less demanding deuterium for protium results in rate accelerations for these processes. Herein, we use deuterium substitution in a cationic guest molecule to probe the sensitivity limits of the guest exchange process from a highly-charged supramolecular host.

  10. Distribution of uranium, thorium, and isotopic composition of uranium in soil samples of south Serbia: Evidence of depleted uranium

    OpenAIRE

    Sahoo Sarata Kumar; Fujimoto Kenzo; Čeliković Igor; Ujić Predrag; Žunić Zora S.

    2004-01-01

    Inductively coupled plasma mass spectrometry and thermal ionization mass spectrom - etry were used to measure concentration of uranium and thorium as well as isotopic composition of uranium respectively in soil samples collected around south Serbia. An analytical method was established for a routine sample preparation procedure for uranium and thorium. Uranium was chemically separated and purified from soil samples by anion exchange resin and UTEVA extraction chromatography and its isotopic c...

  11. Isotopic structure of Lake Whitefish in Lake Huron: Evidence for regional and local populations based on resource use

    Science.gov (United States)

    Eberts, Rebecca L.; Wissel, Bjorn; Simpson, Gavin L.; Crawford, Stephen S.; Stott, Wendylee; Hanner, Robert H.; Manzon, Richard G.; Wilson, Joanna Y.; Boreham, Douglas R.; Somers, Christopher M.

    2017-01-01

    Lake Whitefish Coregonus clupeaformis is the most commercially valuable species in Lake Huron. The fishery for this species has historically been managed based on 25 management units (17 in Canada, 8 in the USA). However, congruence between the contemporary population structure of Lake Whitefish and management units is poorly understood. We used stable isotopes of carbon (δ13C) and nitrogen (δ15N), food web markers that reflect patterns in resource use (i.e., prey, location, habitat), to assess the population structure of spawning-phase Lake Whitefish collected from 32 sites (1,474 fish) across Lake Huron. We found large isotopic variation among fish from different sites (ranges: δ13C = 10.2‰, δ15N = 5.5‰) and variable niche size and levels of overlap (standard ellipse area = 1.0–4.3‰2). Lake Huron contained spawning-phase fish from four major isotopic clusters largely defined by extensive variation in δ13C, and the isotopic composition of fish sampled was spatially structured both within and between lake basins. Based on cluster compositions, we identified six putative regional groups, some of which represented sites of high diversity (three to four clusters) and others with less (one to two clusters). Analysis of isotopic values from Lake Whitefish collected from summer feeding locations and baseline prey items showed similar isotopic variation and established spatial linkage between spawning-phase and summer fish. Our results show that summer feeding location contributes strongly to the isotopic structure we observed in spawning-phase fish. One of the regional groups we identified in northern Georgian Bay is highly distinct based on isotopic composition and possibly ecologically unique within Lake Huron. Our findings are congruent with several previous studies using different markers (genetics, mark–recapture), and we conclude that current management units are generally too small and numerous to reflect the population structure of Lake Whitefish

  12. Isotope effects on L-H threshold and confinement in tokamak plasmas

    Science.gov (United States)

    Maggi, C. F.; Weisen, H.; Hillesheim, J. C.; Chankin, A.; Delabie, E.; Horvath, L.; Auriemma, F.; Carvalho, I. S.; Corrigan, G.; Flanagan, J.; Garzotti, L.; Keeling, D.; King, D.; Lerche, E.; Lorenzini, R.; Maslov, M.; Menmuir, S.; Saarelma, S.; Sips, A. C. C.; Solano, E. R.; Belonohy, E.; Casson, F. J.; Challis, C.; Giroud, C.; Parail, V.; Silva, C.; Valisa, M.; Contributors, JET

    2018-01-01

    The dependence of plasma transport and confinement on the main hydrogenic ion isotope mass is of fundamental importance for understanding turbulent transport and, therefore, for accurate extrapolations of confinement from present tokamak experiments, which typically use a single hydrogen isotope, to burning plasmas such as ITER, which will operate in deuterium–tritium mixtures. Knowledge of the dependence of plasma properties and edge transport barrier formation on main ion species is critical in view of the initial, low-activation phase of ITER operations in hydrogen or helium and of its implications on the subsequent operation in deuterium–tritium. The favourable scaling of global energy confinement time with isotope mass, which has been observed in many tokamak experiments, remains largely unexplained theoretically. Moreover, the mass scaling observed in experiments varies depending on the plasma edge conditions. In preparation for upcoming deuterium–tritium experiments in the JET tokamak with the ITER-like Be/W Wall (JET-ILW), a thorough experimental investigation of isotope effects in hydrogen, deuterium and tritium plasmas is being carried out, in order to provide stringent tests of plasma energy, particle and momentum transport models. Recent hydrogen and deuterium isotope experiments in JET-ILW on L-H power threshold, L-mode and H-mode confinement are reviewed and discussed in the context of past and more recent isotope experiments in tokamak plasmas, highlighting common elements as well as contrasting observations that have been reported. The experimental findings are discussed in the context of fundamental aspects of plasma transport models.

  13. Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

    Science.gov (United States)

    Alemayehu, Melesse; Zhang, Hong-Fu; Seitz, Hans-Michael

    2017-10-01

    Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary volcanic rocks of southern Ethiopian rift (Dillo and Megado) reveal the influence of late stage melt-peridotite interaction on the early depleted and variably metasomatized lithospheric mantle. Two types of lherzolites are reported (LREE-depleted La/Sm(N) = 0.11-0.37 × Cl and LREE-enriched, La/Sm(N) = 1.88-15.72 × Cl). The depleted lherzolites have variable range in Li concentration (olivine: 2.1-5.4 ppm; opx: 1.1-2.3 ppm; cpx: 1.0-1.8 ppm) and in Li isotopic composition (δ7Li in olivine: -9.4 to 1.5‰; in opx: -4.5 to 3.6‰; in cpx: -17.0 to 4.8‰), indicating strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The enriched lherzolites have limited range in both Li abundances (olivine: 2.7-3.0 ppm; opx: 1.1-3.1 ppm; cpx: 1.1-2.3 ppm) and Li isotopic compositions (δ7Li in olivine: -1.3 to +1.3‰; in opx: -2.0 to +5.0‰; in cpx: -7.5 to +4.8‰), suggest that the earlier metasomatic event which lead to LREE enrichment could also homogenize the Li contents and its isotopes. The enriched harzburgite and clinopyroxenite minerals show limited variation in Li abundances and variable Li isotopic compositions. The Li enrichments of olivine and clinopyroxene correlate neither with the incompatible trace element enrichment nor with the Sr-Nd isotopic compositions of clinopyroxene. These observations indicate that the metasomatic events which are responsible for the LREE enrichment and for the Li addition are distinct, whereby the LREE-enrichment pre-dates the influx of Li. The presence of large Li isotopic disequilibria within and between minerals of depleted and enriched peridotites suggest that the lithospheric mantle beneath the southern Ethiopian rift has experienced recent melt-peridotite interaction. Thus, the Li data set reported in this study offer new

  14. Lead isotopic evidence for interaction between plume and lower crust during emplacement of peralkaline Lovozero rocks and related rare-metal deposits, East Fennoscandia, Kola Peninsula, Russia

    Science.gov (United States)

    Zartman, R. E.; Kogarko, L. N.

    2017-05-01

    country rock provides strong evidence that this old lower crust was the contaminant responsible for the deviation of the Lovozero rocks from a presumed original FOZO lead isotopic composition. Evaluating the presence of such a lower crustal component in the Lovozero rock samples suggests a 5-10% contamination by such rocks. Contamination by upper crustal rock is limited to only a negligible amount.

  15. North Atlantic Deep Water export to the Southern Ocean over the past 14 Myr: Evidence from Nd and Pb isotopes in ferromanganese crusts

    Science.gov (United States)

    Frank, M.; Whiteley, N.; Kasten, S.; Hein, J.R.; O'Nions, K.

    2002-01-01

    The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

  16. Titanium isotopes and rare earth patterns in CAIs: Evidence for thermal processing and gas-dust decoupling in the protoplanetary disk

    Science.gov (United States)

    Davis, Andrew M.; Zhang, Junjun; Greber, Nicolas D.; Hu, Jingya; Tissot, François L. H.; Dauphas, Nicolas

    2018-01-01

    Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to 49Ti/47Ti, we found that ε50Ti values are somewhat variable among CAIs, and that ε46Ti is highly correlated with ε50Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between ε46Ti and ε50Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ‧49Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ‧49Ti is from ∼-4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

  17. Preliminary Failure Modes, Effects and Criticality Analysis (FMECA) of the conceptual Brayton Isotope Power System (BIPS) Flight System

    International Nuclear Information System (INIS)

    Miller, L.G.

    1976-01-01

    A failure modes, effects and criticality analysis (FMECA) was made of the Brayton Isotope Power System Flight System (BIPS-FS) as presently conceived. The components analyzed include: Mini-BRU; Heat Source Assembly (HSA); Mini-Brayton Recuperator (MBR); Space Radiator; Ducts and Bellows, Insulation System; Controls; and Isotope Heat Source (IHS)

  18. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël [Laboratoire de Glaciologie et Géophysique de l’Environnement, CNRS, F-38041 Grenoble (France); Univ. Grenoble Alpes, LGGE, F-38041 Grenoble (France); Meusinger, Carl; Johnson, Matthew S. [Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Jost, Rémy [Laboratoire de Interdisciplinaire de Physique (LIPHY) Univ. de Grenoble, Grenoble (France); Bhattacharya, S. K. [Research Center for Environmental Changes, Academia Sinica, Nangang, Taipei 115, Taiwan (China)

    2014-06-28

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying

  19. Isotope evidence for the microbially mediated formation of elemental sulfur: A case study from Lake Peten Itza, Guatemala

    Science.gov (United States)

    Turchyn, A. V.; Bennett, V. A.; Hodell, D. A.

    2013-12-01

    Elemental, or native, sulfur nodules or veins can be formed during aqueous diagenesis and have been found in a range of natural environments, including lake sediments. What governs the formation of elemental sulfur remains enigmatic, although it is widely thought to be microbially-mediated. While most of the literature suggests elemental sulfur is formed by partial re-oxidation of hydrogen sulphide, elemental sulfur can also form during incomplete bacterial sulfate reduction or during aborted sulfur disproportionation. Lake Peten Itza, in Northern Guatemala, which was cored during the International Continental Drilling program in 2006, is one of the few places where elemental sulfur nodules are forming during microbial diagenesis today. Sulfur isotopes are strongly partitioned during bacterial sulfate reduction and the magnitude of the partitioning yields insight into the microbial reactions and environmental conditions. For example, sulfate reduction that terminates at elemental sulfur likely requires the use of the intracellular trithonite pathway, which may drive larger overall sulfur isotope fractionation between the precursor sulfate and the elemental sulfur product. Sulfur isotopes combined with oxygen isotopes in the precursor sulfate may provide even more information about microbial mechanisms. We present coupled pore fluid sulfate concentrations and sulfur and oxygen isotope measurements, as well as co-existing nodule sulfur isotopes from the Lake Peten Itza sediments. The δ34S of the nodules in the lake sediments ranges from +12 to -13‰, often within a single nodule. This suggests formation from an open system where sulfate is replenished by diffusion, as might be expected during pore fluid diagenesis. The δ34S of the pore fluid sulfate at the depth of nodule formation is between 50 and 60‰ (versus the precursor gypsum which is 17 to 18‰) suggesting a large sulfur isotope fractionation between sulfate and elemental sulfur (38 to 73‰). Pyrite was

  20. Solvent effects and secondary isotope effects for probing diradical character in the thermal decarboxylation of β-peroxylactones

    International Nuclear Information System (INIS)

    Adam, W.; Cueto, O.; Guedes, L.N.; Rodriguez, L.O.

    1978-01-01

    The lack of solvent effects in the activation parameters and product distribution and the lack of secondary deuterium isotope effects at the α-carbon and β-alkyl migrant substantiates that the thermal decarboxylation of β-peroxy lactones proceeds via a 1,5-diradical

  1. Assessment of the effects of cage fish-farming on damselfish-associated food chains using stable-isotope analyses

    International Nuclear Information System (INIS)

    Jan, Rong-Quen; Kao, Shuh-Ji; Dai, Chang-Feng; Ho, Cheng-Tze

    2014-01-01

    Highlights: • Damselfishes living at sites near a cage farm bore lower δ 13 C and higher δ 15 N. • Similar trends occurred in zooplankton and detritus, major foods for damselfishes. • δ 15 N enrichment in fish may have arisen from the uptake of excess feed and prey. • Farm wastes were documented entering the ecosystem through the pelagic food chain. • No clear evidence of the effects of cage farming on stable isotopes in macroalgae. - Abstract: To assess the effect of cage fish-farming on the coral reef ecosystem off Xiaoliuchiu Island, southern Taiwan, geographical differences in the food chain of each of two damselfishes, Pomacentrus vaiuli and Chromis margaritifer, were examined using a stable-isotope approach. For each damselfish, individuals were found to consume similar foods at all sites. However, specimens collected at sites near the cage farm (as the experimental sites) exhibited lower δ 13 C and higher δ 15 N signatures compared to those from reference sites. Similar trends also occurred in the zooplankton and detritus, two major food sources for both damselfishes. This finding indicates that particulate organic matter released by the farm may have entered the coral reef ecosystem through the pelagic food chain. Artificial reef emplacement is recommended to provide extra habitats under cage farms to support additional pelagic-feeding fish populations, thereby reducing environmental impacts of cage farming on coral reefs

  2. Deuterium isotope effects on 13C chemical shifts of negatively charged NH.N systems

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Pietrzak, Mariusz; Grech, Eugeniusz

    2013-01-01

    ” and equilibrium cases. NMR assignments of the former have been revised. The NH proton is deuteriated. The isotope effects on 13C chemical shifts are rather unusual in these strongly hydrogen bonded systems between a NH and a negatively charged nitrogen atom. The formal four-bond effects are found to be negative......Deuterium isotope effects on 13C chemical shifts are investigated in anions of 1,8-bis(4-toluenesulphonamido)naphthalenes together with N,N-(naphthalene-1,8-diyl)bis(2,2,2-trifluoracetamide) all with bis(1,8-dimethylamino)napthaleneH+ as counter ion. These compounds represent both “static...... indicating transmission via the hydrogen bond. In addition, unusual long range effects are seen. Structures, 1H and 13C NMR chemical shifts and changes in nuclear shieldings upon deuteriation are calculated using density functional theory methods...

  3. Pleistocene paleo-groundwater as a pristine fresh water resource in southern Germany – evidence from stable and radiogenic isotopes

    International Nuclear Information System (INIS)

    Geldern, Robert van; Baier, Alfons; Subert, Hannah L.; Kowol, Sigrid; Balk, Laura; Barth, Johannes A.C.

    2014-01-01

    Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ∼20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management. - Highlights: • Groundwater from deep aquifer identified as paleo-water with age over 20,000 years. • Low stable isotope values indicate recharge during Pleistocene. • Shallow aquifer mirrors stable isotope signature of average modern precipitation. • Identification of non-renewable paleo-waters enhance sustainable water management. • Strict protection measures of authorities justified by isotope geochemistry

  4. Dose formation and hematologic effects with prolonged internal exposure of rats by isotope 131I

    International Nuclear Information System (INIS)

    Sova, O.A.; Drozd, Yi.P.

    2013-01-01

    Processes in single dose formation and long-term domestic revenue 131 I in rats was investigated. Original method of estimating absorbed doses in hemacyte for macro-dosemeters indicators was proposed. Dose factors for hemacyte and the dynamics of the blood-forming organs doses for prolonged two cases of prolonged exposure was calculated. Hematologic effects were studied for two variants of entry of the isotope. Peculiarities of doses formation and identified hematological effects are discussed

  5. Femtometer accuracy EXAFS measurements: Isotopic effect in the first, second and third coordination shells of germanium

    Energy Technology Data Exchange (ETDEWEB)

    Purans, J; Timoshenko, J; Kuzmin, A [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Dalba, G; Fornasini, P; Grisenti, R; Afify, N D [Dip. di Fisica dell' Universita di Trento, Via Sommarive 14, I-38050 Povo, Trento (Italy); Rocca, F [Istituto di Fotonica e Nanotecnologie del CNR, Sezione ' FBK-CeFSA' di Trento, Povo, Trento (Italy); De Panfilis, S [Research Center Soft INFM-CNR, c/o Universita di Roma La Sapienza, I-00185 Roma (Italy); Ozhogin, I [Institute of Molecular Physics, Russian Research Centre ' Kurchatov Institute' , 123182 Moscow (Russian Federation); Tiutiunnikov, S I, E-mail: purans@cfi.lu.l [Joint Institute for Nuclear Research, 141980 Dubna, Moscow Region (Russian Federation)

    2009-11-15

    The analysis of the EXAFS signals from {sup 70}Ge and {sup 76}Ge has evidenced the low-temperature effect of isotopic mass difference on the amplitude of relative atomic vibrations. This effect is reflected in the difference of the Debye-Waller factors of the first three coordination shells, and on the difference of nearest-neighbour average interatomic distances, evaluated with femtometer accuracy. The experimental results are in agreement with theoretical expectations.

  6. Effect of Ca content on equilibrium Ca isotope fractionation between orthopyroxene and clinopyroxene

    Science.gov (United States)

    Wang, Wenzhong; Zhou, Chen; Qin, Tian; Kang, Jin-Ting; Huang, Shichun; Wu, Zhongqing; Huang, Fang

    2017-12-01

    Concentration effect on equilibrium inter-mineral isotope fractionation is ubiquitous in solid solution systems, but it is not clear in which concentration range such effect is prominent. Using first-principles calculations, we examine the effect of Ca and Fe contents in orthopyroxene (opx) on its average Casbnd O bond length and the equilibrium Ca isotope fractionation factor (103lnα) between opx and clinopyroxene (cpx). Our results reveal that the average Casbnd O bond length in opx is much smaller than that in cpx and it does not change with variable Ca content x (x and y are mole ratios in CaxFeyMg1-x-ySiO3 thereafter here) when x ≤ 1/48. Incorporation of Fe (y ≥ 1/32) into opx with a fixed Ca content can only slightly increase the average Casbnd O bond length. 103lnαopx-cpx of 44Ca/40Ca is linearly correlated with the average Casbnd O bond length in opx, suggesting that 103lnαopx-cpx of 44Ca/40Ca is controlled by opx Casbnd O bond strength. Our calculations indicate that the Ca concentration effect on 103lnαopx-cpx is significant when x in opx ranges from 2/16 to 1/48, while Fe in natural opx only causes a slight decrease in 103lnαopx-cpx. Our results provide insights into Ca isotope fractionation in high-temperature geochemical processes. Given that Ca content x in opx from natural peridotites is usually lower than 1/32 and Fe content y is generally ∼10 mol%, Ca and Fe concentration effects on 103lnαopx-cpx in natural samples are negligible. Rather, 103lnαopx-cpx is mainly controlled by temperature. 103lnαopx-cpx of 44Ca/40Ca decreases from 0.50‰ to 0.26‰ when temperature increases from 1000 K to 1400 K if the Fe effect is taken into account. Therefore, if Ca isotope fractionation between opx and cpx (Δ44/40Caopx-cpx) in natural peridotites is greater than 0.50‰ or lower than 0.26‰, it may indicate disequilibrium of Ca isotopes. Finally, the large 103lnαopx-cpx relative to our current analytical precision suggests that Δ44/40Caopx

  7. Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, M.; Baba, A. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Kawamura, Y.; Nishi, M.

    1998-03-01

    Though lithium ceramic materials such as Li{sub 2}O, LiAlO{sub 2}, Li{sub 2}ZrO{sub 3}, Li{sub 2}TiO{sub 3} and Li{sub 4}SiO{sub 4} are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H{sub 2} and D{sub 2}O or that between D{sub 2} and H{sub 2}O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li{sub 2}ZrO{sub 3} blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

  8. Who is who matters-The effects of pseudoreplication in stable isotope analyses.

    Science.gov (United States)

    Mundry, Roger; Oelze, Vicky M

    2016-10-01

    Stable isotope analysis in free-ranging primates is a promising new avenue in reconstructing feeding niches and temporal dietary variation. Particularly, the large sample sizes obtained from non-invasively collected hair and fecal samples from nests of great apes offer great potential. However, analyzing repeated observations of the same individuals without controlling for potential differences among them means to "pseudoreplicate" and can lead to a greatly inflated probability of erroneous significance. We here test the effects of pseudoreplication in stable isotope data of great ape hair by means of simulations. We show that pseudoreplication can severely affect the probability of erroneous significance as well as non-significance. We suggest several strategies to avoid pseudoreplication in primate isotope ecology. First, if applicable, information on individual identity should be included in statistical analyses. Second, if samples derive from unhabituated animals, sampling at far apart locations or territories should avoid resampling of the same animal. In great apes, sampling of independent nests within nest groups can ensure that each sample derives from a different individual. Third, we encourage the combination of genetic surveys with sampling for isotope analyses to ensure the (genetic) identification of individuals. Am. J. Primatol. 78:1017-1030, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  9. Magnitude of intrinsic isotope effects in the dopamine beta-monooxygenase reaction.

    Science.gov (United States)

    Miller, S M; Klinman, J P

    1983-06-21

    Intrinsic primary hydrogen isotope effects (kH/kD) have been obtained for the carbon-hydrogen bond cleavage step catalyzed by dopamine beta-monooxygenase. Irreversibility of this step is inferred from the failure to observe back-exchange of tritium from TOH into substrate under conditions of dopamine turnover; this result cannot be due to solvent inaccessibility at the enzyme active site, since we will demonstrate [Ahn, N., & Klinman, J. P. (1983) Biochemistry (following paper in this issue)] that a solvent-derived proton or triton must be at the enzyme active site prior to substrate activation. As shown by Northrop [Northrop, D. B. (1975) Biochemistry 14, 2644], for enzymatic reactions in which the carbon-hydrogen bond cleavage step is irreversible, comparison of D(V/K) to T(V/K) allows an explicit solution for kH/kD. Employing a double-label tracer method, we have been able to measure deuterium isotope effects on Vmax/Km with high precision, D(V/K) = 2.756 +/- 0.054 at pH 6.0. The magnitude of the tritium isotope effect under comparable experimental conditions is T(V/K) = 6.079 +/- 0.220, yielding kH/kD = 9.4 +/- 1.3. This result was obtained in the presence of saturating concentrations of the anion activator fumarate. Elimination of fumarate from the reaction mixture leads to high observed values for isotope effects on Vmax/Km, together with an essentially invariant value for kH/kD = 10.9 +/- 1.9. Thus, the large disparity between isotope effects, plus or minus fumarate, cannot be accounted for by a change in kH/kD, and we conclude a role for fumarate in the modulation of the partitioning of enzyme-substrate complex between catalysis and substrate dissociation. On the basis of literature correlations of primary hydrogen isotope effects and the thermodynamic properties of hydrogen transfer reactions, the very large magnitude of kH/kD = 9.4-10.9 for dopamine beta-monooxygenase suggests an equilibrium constant not very far from unity for the carbon-hydrogen bond

  10. Isotopic discrimination factors and nitrogen turnover rates in reared Atlantic bluefin tuna larvae (Thunnus thynnus: effects of maternal transmission

    Directory of Open Access Journals (Sweden)

    Amaya Uriarte

    2016-11-01

    Full Text Available The use of stable isotope analysis to study animal diets requires estimates of isotopic turnover rates (half time, t50 and discrimination factors (Δ for an accurate interpretation of trophic patterns. The stable isotopes of carbon and nitrogen were analysed for eggs and reared larvae of Thunnus thynnus, as well as for the different diets supplied during the experiment. The results showed high values of δ15N in eggs and larvae (n=646 until 4 DAH. After this time lapse, the stable isotope values declined progressively until 12 DAH, when notochord flexion began. The δ13C showed an inverse trend, suggesting that maternal inheritance of the stable isotopes is evident until pre-flexion stages. This study proposes a model for estimating maternal isotopic signatures of bluefin broodstock. After notochord flexion, larvae were fed with aquaculture-bred gilthead seabream, which resulted in a rapid increase of bluefin larvae δ15N values together with a rapid decrease in δ13C values. The estimated nitrogen half-time to reach the steady state from the diet was 2.5±0.3 days and the discrimination factor was 0.4±0.3(‰. These results represent the first data set that has allowed isotopic nitrogen turnover rates and discrimination factors of the larval stages of bluefin tuna to be estimated.

  11. Food sources of the pearl oyster in coastal ecosystems of Japan: Evidence from diet and stable isotope analysis

    Science.gov (United States)

    Fukumori, Kayoko; Oi, Misa; Doi, Hideyuki; Okuda, Noboru; Yamaguchi, Hitomi; Kuwae, Michinobu; Miyasaka, Hitoshi; Yoshino, Kenji; Koizumi, Yoshitsugu; Omori, Koji; Takeoka, Hidetaka

    2008-02-01

    We estimated the composition of two food sources for the cultured pearl oyster Pinctada fucata martensii using stable isotopes and stomach content analysis in the coastal areas of the Uwa Sea, Japan. The δ13C values of oysters (-17.5 to -16.8‰) were intermediate between that of particulate organic matter (POM, -20.2 to -19.1‰) and attached microalgae on pearl cages (-13.0‰). An isotope mixing model suggested that oysters were consuming 78% POM (mainly phytoplankton) and 22% attached microalgae. The attached microalgal composition of the stomach content showed a strong resemblance to the composition of that estimated through the isotope mixing model, suggesting preferential utilization of specific components is unlikely in this species. These results indicate that P. fucata martensii feed on a mixture of phytoplankton and attached microalgae, and that the attached microalgae on pearl cages can serve as an important additional food source.

  12. Coupled S and Sr isotope evidences for elevated arsenic concentrations in groundwater from the world's largest antimony mine, Central China

    Science.gov (United States)

    Wen, Bing; Zhou, Aiguo; Zhou, Jianwei; Liu, Cunfu; Huang, Yuliu; Li, Ligang

    2018-02-01

    The Xikuangshan(XKS) mine, the world's largest antimony mine, was chosen for a detailed arsenic hydrogeochemical study because of the elevated arsenic in bedrock aquifers used by local residents. Hydrochemical data, δ34S values of dissolved SO42- and 87Sr/86Sr ratios have been analyzed to identify the predominant geochemical processes that control the arsenic mobilization within the aquifers. Groundwater samples can be divided into three major types: low arsenic groundwater (0-50 μg/L), high arsenic groundwater (50-1000 μg/L) and anomalous high arsenic groundwater (>1000 μg/L). Arsenic occurs under oxidizing conditions at the XKS Sb mine as the HAsO42- anion. The Ca/Na ratio correlates significantly with HCO3-/Na and Sr/Na ratios, indicating that carbonate dissolution and silicate weathering are the dominant processes controlling groundwater hydrochemistry. The δ34S values of the groundwater indicate that dissolved SO42- in groundwater is mainly sourced from the oxidation of sulfide minerals, and elevated As concentrations in groundwater are influenced by the mixing of mine water and surface water. Furthermore, the δ34S values are not correlated with dissolved As concentrations and Fe concentrations, suggesting that the reduction dissolution of Fe(III) hydroxides is not the dominant process controlling As mobilization. The 87Sr/86Sr ratios imply that elevated As concentrations in groundwater are primarily derived from the interaction with the stibnite and silicified limestone. More specifically, the excess-Na ion, the feature of Ca/Na ratio, and the spatial association of elevated As concentrations in groundwater collectively suggest that high and anomalous high arsenic groundwater are associated with smelting slags and, in particular, the arsenic alkali residue. In general, the hydrochemistry analysis, especially the S and Sr isotope evidences elucidate that elevated As concentrations and As mobilization are influenced by several geochemical processes

  13. Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

    Science.gov (United States)

    Burruss, R.C.; Laughrey, C.D.

    2010-01-01

    During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

  14. An experiment to assess the effects of diatom dissolution on oxygen isotope ratios.

    Science.gov (United States)

    Smith, Andrew C; Leng, Melanie J; Swann, George E A; Barker, Philip A; Mackay, Anson W; Ryves, David B; Sloane, Hilary J; Chenery, Simon R N; Hems, Mike

    2016-01-30

    Current studies which use the oxygen isotope composition from diatom silica (δ(18) Odiatom ) as a palaeoclimate proxy assume that the δ(18) Odiatom value reflects the isotopic composition of the water in which the diatom formed. However, diatoms dissolve post mortem, preferentially losing less silicified structures in the water column and during/after burial into sediments. The impact of dissolution on δ(18) Odiatom values and potential misinterpretation of the palaeoclimate record are evaluated. Diatom frustules covering a range of ages (6 samples from the Miocene to the Holocene), environments and species were exposed to a weak alkaline solution for 48 days at two temperatures (20 °C and 4 °C), mimicking natural dissolution post mucilage removal. Following treatment, dissolution was assessed using scanning electron microscope images and a qualitative diatom dissolution index. The diatoms were subsequently analysed for their δ(18) O values using step-wise fluorination and isotope ratio mass spectrometry. Variable levels of diatom dissolution were observed between the six samples; in all cases higher temperatures resulted in more frustule degradation. Dissolution was most evident in younger samples, probably as a result of the more porous nature of the silica. The degree of diatom dissolution does not directly equate to changes in the isotope ratios; the δ(18) Odiatom value was, however, lower after dissolution, but in only half the samples was this reduction outside the analytical error (2σ analytical error = 0.46‰). We have shown that dissolution can have a small negative impact on δ(18) Odiatom values, causing reductions of up to 0.59‰ beyond analytical error (0.46‰) at natural environmental temperatures. These findings need to be considered in palaeoenvironmental reconstructions using δ(18) Odiatom values, especially when interpreting variations in these values of <1‰. Copyright © 2015 John Wiley & Sons, Ltd.

  15. Effects of Brine Salinity on Clumped Isotopes and Implications for Applications to Carbonate Diagenesis

    Science.gov (United States)

    Kluge, T.; John, C. M.; Jourdan, A.

    2012-12-01

    Carbonate clumped isotope thermometry relies on the overabundance of 13C-18O bonds in the crystal lattice compared to a stochastic distribution and was calibrated in laboratory experiments using carbonates precipitated from (mainly) de-ionized water that was supersaturated with calcium carbonate (Ghosh et al., 2006). However, the clumped isotope method has also been applied to carbonates that precipitated in the marine and subsurface environments from fluids with significant salt concentrations. These saline fluids differ markedly from the solution used for laboratory calibration. Variations in the electro-chemical potential due to changes in the ion composition and concentration of the solution could influence the physical properties of the clumped isotope bonding and lead to deviations from the commonly used temperature calibration. Consequently, calibrations at high salinities and high temperatures are needed to confidently extend the application of clumped isotopes to diagenetic processes. We investigated the effect of salinity on clumping by precipitating carbonates (mainly calcite) in the laboratory between 23 and 90 °C using a setup analogous to the experiments of Ghosh et al. (2006). A first subset of experiments was performed at low salinities, while during a second subset of experiments we saturated the solution with NaCl (about 35 g/100 ml) in order to mimic a highly saline brine. Since the same experimental procedures were used for both sub-sets (same temperatures of precipitation and rates of nitrogen gas bubbling), we can directly compare clumped isotope values in highly saline versus low-salinity solutions. The initial clumped isotope results obtained from the brine solution agree within uncertainty with results from carbonates precipitated from a NaCl-free solution at the same temperatures. This suggests that clumped isotopes can be applied to carbonates precipitated under highly saline conditions. We acknowledge the financial support of QCCSRC

  16. Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

    Science.gov (United States)

    Deng, Yuying; Li, Yingzhou; Li, Long

    2018-04-01

    Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

  17. Molecular isotopic evidence for anaerobic oxidation of methane in deep-sea hydrothermal vent environment in Okinawa Trough

    Science.gov (United States)

    Uchida, M.; Takai, K.; Inagaki, F.

    2003-04-01

    Large amount of methane in anoxic marine sediments as well as cold seeps and hydrothermal vents is recycled through for an anoxic oxidation of methane processes. Now that combined results of field and laboratory studies revealed that microbiological activity associated with syntrophic consortium of archaea performing reversed methanogenesis and sulfate-reducing bacteria is significant roles in methane recycling, anaerobic oxidation of methane (AOM). In this study, we examined the diversity of archaeal and bacterial assemblages of AOM using compound-specific stable carbon isotopic and phylogenetic analyses. "Iheya North" in Okinawa Trough is sediment-rich, back arc type hydrothermal system (27^o47'N, 126^o53'E). Sediment samples were collected from three sites where are "bubbling sites", yellow-colored microbial mats are formed with continuous bubbling from the seafloor bottom, vent mussel's colonies site together with slowly venting and simmering, and control site off 100 m distance from thermal vent. This subsea floor structure has important effect in the microbial ecosystem and interaction between their activity and geochemical processes in the subseafloor habitats. Culture-independent, molecular biological analysis clearly indicated the presence of thermophilic methanogens in deeper area having higher temperatures and potential activity of AMOs consortium in the shallower area. AMO is composed with sulfate-reducing bacterial components (Desulfosarcina spp.) and anoxic methane oxidizing archaea (ANME-2). These results were consistent with the results of compound-specific carbon analysis of archaeal biomarkers. They showed extremely depleted 13C contents (-80 ppm ˜ -100 ppm), which also appeared to be capable of directly oxidizing methane.

  18. Enzymatic Kinetic Isotope Effects from Path-Integral Free Energy Perturbation Theory.

    Science.gov (United States)

    Gao, J

    2016-01-01

    Path-integral free energy perturbation (PI-FEP) theory is presented to directly determine the ratio of quantum mechanical partition functions of different isotopologs in a single simulation. Furthermore, a double averaging strategy is used to carry out the practical simulation, separating the quantum mechanical path integral exactly into two separate calculations, one corresponding to a classical molecular dynamics simulation of the centroid coordinates, and another involving free-particle path-integral sampling over the classical, centroid positions. An integrated centroid path-integral free energy perturbation and umbrella sampling (PI-FEP/UM, or simply, PI-FEP) method along with bisection sampling was summarized, which provides an accurate and fast convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. The PI-FEP method is illustrated by a number of applications, to highlight the computational precision and accuracy, the rule of geometrical mean in kinetic isotope effects, enhanced nuclear quantum effects in enzyme catalysis, and protein dynamics on temperature dependence of kinetic isotope effects. © 2016 Elsevier Inc. All rights reserved.

  19. Controls of evaporative irrigation return flows in comparison to seawater intrusion in coastal karstic aquifers in northern Sri Lanka: Evidence from solutes and stable isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Chandrajith, Rohana, E-mail: rohanac@pdn.ac.lk [Department of Geology, Faculty of Science, University of Peradeniya (Sri Lanka); Diyabalanage, Saranga [Department of Geology, Faculty of Science, University of Peradeniya (Sri Lanka); Premathilake, K.M. [Water Supply and Drainage Board, Telewala Road, Ratmalana (Sri Lanka); Hanke, Christian; Geldern, Robert van; Barth, Johannes A.C. [Friedrich-Alexander University Erlangen-Nuremberg (FAU), Department of Geography and Geosciences, GeoZentrum Nordbayern, Schlossgarten 5, 91054 Erlangen (Germany)

    2016-04-01

    Groundwater in Miocene karstic aquifers in the Jaffna Peninsula of Sri Lanka is an important resource since no other fresh water sources are available in the region. The subsurface is characterized by highly productive limestone aquifers that are used for drinking and agriculture purposes. A comprehensive hydrogeochemical study was carried out to reveal the processes affecting the groundwater quality in this region. Major and trace element composition and environmental isotope ratios of oxygen and hydrogen (δ{sup 18}O{sub H2O} and δ{sup 2}H{sub H2O}) were determined in 35 groundwater samples for this investigation. The ion abundance of groundwater in the region was characterized by an anion sequence order with HCO{sub 3}¯ > Cl¯ > SO{sub 4}¯ > NO{sub 3}¯. For cations, average Na{sup +}+K{sup +} contents in groundwater exceeded those of Ca{sup 2+} + Mg{sup 2+} in most cases. Ionic relationships of major solutes indicated open system calcite dissolution while seawater intrusions are also evident but only close to the coast. The solute contents are enriched by agricultural irrigation returns and associated evaporation. This was confirmed by the stable isotope composition of groundwater that deviated from the local meteoric water line (LMWL) and formed its own regression line denoted as the local evaporation line (LEL). The latter can be described by δ{sup 2}H{sub H2O} = 5.8 × δ{sup 18}O{sub H2O-–} 2.9. Increased contents of nitrate-N (up to 5 mg/L), sulfate (up to 430 mg/L) and fluoride (up to 1.5 mg/L) provided evidences for anthropogenic inputs of solutes, most likely from agriculture activities. Among trace elements Ba, Sr, As and Se levels in the Jaffna groundwater were higher compared to that of the dry zone metamorphic aquifers in Sri Lanka. Solute geochemistry and stable isotope evidences from the region indicates that groundwater in the area is mainly derived from local modern precipitation but modified heavily by progressive evaporative

  20. Isotope effects in ice Ih: A path-integral simulation

    OpenAIRE

    Herrero, Carlos P.; Ramirez, Rafael

    2011-01-01

    Ice Ih has been studied by path-integral molecular dynamics simulations, using the effective q-TIP4P/F potential model for flexible water. This has allowed us to analyze finite-temperature quantum effects in this solid phase from 25 to 300 K at ambient pressure. Among these effects we find a negative thermal expansion of ice at low temperatures, which does not appear in classical molecular dynamics simulations. The compressibility derived from volume fluctuations gives results in line with ex...

  1. Isotope effect in quasi-two-dimensional metal-organic antiferromagnets

    Science.gov (United States)

    Goddard, P. A.; Singleton, J.; Maitland, C.; Blundell, S. J.; Lancaster, T.; Baker, P. J.; McDonald, R. D.; Cox, S.; Sengupta, P.; Manson, J. L.; Funk, K. A.; Schlueter, J. A.

    2008-08-01

    Although the isotope effect in superconducting materials is well documented, changes in the magnetic properties of antiferromagnets due to isotopic substitution are seldom discussed and remain poorly understood. This is perhaps surprising given the possible link between the quasi-two-dimensional (Q2D) antiferromagnetic and superconducting phases of the layered cuprates. Here we report the experimental observation of shifts in the Néel temperature and critical magnetic fields (ΔTN/TN≈4%;ΔBc/Bc≈4%) in a Q2D organic molecular antiferromagnet on substitution of hydrogen for deuterium. These compounds are characterized by strong hydrogen bonds through which the dominant superexchange is mediated. We evaluate how the in-plane and interplane exchange energies evolve as the atoms of hydrogen on different ligands are substituted, and suggest a possible mechanism for this effect in terms of the relative exchange efficiency of hydrogen and deuterium bonds.

  2. Isotope effect studies of the chemical mechanism of nicotinamide adenine dinucleotide malic enzyme from Crassula

    International Nuclear Information System (INIS)

    Grissom, C.B.; Willeford, O.; Wedding, R.T.

    1987-01-01

    The 13 C primary kinetic isotope effect on the decarboxylation of malate by nicotinamide adenine dinucleotide malic enzyme from Crassula argentea is 1.0199 +/- 0.0006 with proteo L-malate-2-H and 1.0162 +/- 0.0003 with malate-2-d. The primary deuterium isotope effect is 1.45 +/- 0.10 on V/K and 1.93 +/- 0.13 on V/sub max/. This indicates a stepwise conversion of malate to pyruvate and CO 2 with hydride transfer preceding decarboxylation, thereby suggesting a discrete oxaloacetate intermediate. This is in agreement with the stepwise nature of the chemical mechanism of other malic enzymes despite the Crassula enzyme's inability to reduce or decarboxylate oxaloacetate. Differences in morphology and allosteric regulation between enzymes suggest specialization of the Crassula malic enzyme for the physiology of crassulacean and acid metabolism while maintaining the catalytic events founds in malic enzymes from animal sources

  3. Isotope effects in aqueous solvation of simple halides

    Science.gov (United States)

    Videla, Pablo E.; Rossky, Peter J.; Laria, D.

    2018-03-01

    We present a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.

  4. 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.

  5. Stable-isotope analysis of a deep-sea benthic-fish assemblage: evidence of an enriched benthic food web.

    Science.gov (United States)

    Boyle, M D; Ebert, D A; Cailliet, G M

    2012-04-01

    In this study, fishes and invertebrates collected from the continental slope (1000 m) of the eastern North Pacific Ocean were analysed using stable-isotope analysis (SIA). Resulting trophic positions (T(P) ) were compared to known diets and habitats from the literature. Dual isotope plots indicated that most species groups (invertebrates and fishes) sorted as expected along the carbon and nitrogen axes, with less intraspecific variability than interspecific variability. Results also indicated an isotopically distinct benthic and pelagic food web, as the benthic food web was more enriched in both nitrogen and carbon isotopes. Trophic positions from SIA supported this finding, resulting in the assignment of fishes to different trophic positions from those expected based on published dietary information. These differences can be explained largely by the habitat of the prey and the percentage of the diet that was scavenged. A mixing model estimated dietary contributions of prey similar to those of the known diet of Bathyraja trachura from stomach-content analysis (SCA). Linear regressions indicated that trophic positions calculated from SIA and SCA, when plotted against B. trachura total length for 32 individuals, exhibited similar variation and patterns. Only the T(P) from SCA yielded significant results (stomach content: P 0·05). © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.

  6. Os-He Isotope Systematics of Iceland Picrites: Evidence for a Deep Origin of the Iceland Plume

    Science.gov (United States)

    Brandon, Alan D.; Graham, David W.; Waight, Tod; Gautason, Bjarni

    2007-01-01

    Recent work on the origin of the Iceland hotspot suggests that it may result from upwelling upper mantle material rather than a deep plume. To constrain the depths of origins of Iceland mantle sources, Os and He isotope systematics were obtained on a suite picrites that span the compositional range observed within the neovolcanic zones.

  7. Oxygen isotopic evidence for accretion of Earth's water before a high-energy Moon-forming giant impact.

    Science.gov (United States)

    Greenwood, Richard C; Barrat, Jean-Alix; Miller, Martin F; Anand, Mahesh; Dauphas, Nicolas; Franchi, Ian A; Sillard, Patrick; Starkey, Natalie A

    2018-03-01

    The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in Δ 17 O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the Δ 17 O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post-giant impact additions to Earth. On the basis of this assumption, our data indicate that post-giant impact additions to Earth could have contributed between 5 and 30% of Earth's water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth's water was accreted before the giant impact and not later, as often proposed.

  8. Oxygen isotopic evidence for accretion of Earth’s water before a high-energy Moon-forming giant impact

    Science.gov (United States)

    Barrat, Jean-Alix; Sillard, Patrick; Starkey, Natalie A.

    2018-01-01

    The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in Δ17O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the Δ17O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post–giant impact additions to Earth. On the basis of this assumption, our data indicate that post–giant impact additions to Earth could have contributed between 5 and 30% of Earth’s water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth’s water was accreted before the giant impact and not later, as often proposed. PMID:29600271

  9. Trophic specialisation of metazoan meiofauna at the Håkon Mosby Mud Volcano: fatty acid biomarker isotope evidence

    NARCIS (Netherlands)

    Van Gaever, S.; Moodley, L.; Pasotti, F.; Houtekamer, M.J.; Middelburg, J.J.; Danovaro, R.; Vanreusel, A.

    2009-01-01

    We report the results of a detailed investigation on the trophoecology of two dominant meiofaunal species at the Håkon Mosby Mud Volcano (HMMV), a deep-sea cold methane-venting seep. Analyses of fatty acids (FAs) and their stable carbon isotopes were used to determine the importance of

  10. Pleistocene paleo-groundwater as a pristine fresh water resource in southern Germany--evidence from stable and radiogenic isotopes.

    Science.gov (United States)

    van Geldern, Robert; Baier, Alfons; Subert, Hannah L; Kowol, Sigrid; Balk, Laura; Barth, Johannes A C

    2014-10-15

    Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ~20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Pb isotope evidence for contaminant-metal dispersal in an international river system: The lower Danube catchment, Eastern Europe

    International Nuclear Information System (INIS)

    Bird, Graham; Brewer, Paul A.; Macklin, Mark G.; Nikolova, Mariyana; Kotsev, Tsvetan; Mollov, Mihail; Swain, Catherine

    2010-01-01

    Lead isotope signatures ( 207 Pb/ 206 Pb, 208 Pb/ 206 Pb, 208 Pb/ 204 Pb, 206 Pb/ 204 Pb), determined by magnetic sector ICP-MS in river channel sediment, metal ores and mine waste, have been used as geochemical tracers to quantify the delivery and dispersal of sediment-associated metals in the lower Danube River catchment. Due to a diverse geology and range of ore-body ages, Pb isotope signatures in ore-bodies within the lower Danube River catchment show considerable variation, even within individual metallogenic zones. It is also possible to discriminate between the Pb isotopic signatures in mine waste and river sediment within river systems draining individual ore bodies. Lead isotopic data, along with multi-element data; were used to establish the provenance of river sediments and quantify sedimentary contributions to mining-affected tributaries and to the Danube River. Data indicate that mining-affected tributaries in Serbia and Bulgaria contribute up to 30% of the river channel sediment load of the lower Danube River. Quantifying relative sediment contributions from mining-affected tributaries enables spatial patterns in sediment-associated metal and As concentrations to be interpreted in terms of key contaminant sources. Combining geochemical survey data with that regarding the provenance of contaminated sediments can therefore be used to identify foci for remediation and environmental management strategies.

  12. Past 20,000-year history of Himalayan aridity: Evidence from oxygen isotope records in the Bay of Bengal

    Digital Repository Service at National Institute of Oceanography (India)

    Chauhan, O.S.

    Late Quaternary climate history of the Himalayas is inferred from sea surface salinity (SSS) changes determined from the oxygen isotope in planktonic foraminifers, in a turbidity-free, 14C-dated core from the Bay of Bengal. The heaviest d18O...

  13. Solvent and solute isotope effects in the aqueous solution of gases. Progress report, July 1, 1978-October 31, 1979

    International Nuclear Information System (INIS)

    Benson, B.B.; Krause, D. Jr.

    1979-10-01

    After developing a 3 He/ 4 He dual beam collection system for the mass spectrometer, the isotopic fractionation factor was determined for helium dissolved in H 2 O, D 2 O, seawater and ethanol. In all solvents the temperature dependence of the fractionation is different from that for a simple isotope vapor pressure effect. Addition of salt to H 2 O increases the fractionation, and the relative salting-out coefficient changes with temperature. A double isotopic effect occurs - the fractionations in D 2 O and H 2 O differ. In ethanol the fractionation is 25% less than in H 2 O

  14. Measurement of isotopic effects in photosynthetic fixation of CO2 by CO2 enriched in carbon 13 and oxygen 18

    International Nuclear Information System (INIS)

    Gerster, Richard

    The use of 13 C and 18 O enriched CO 2 allows to measure with accuracy isotopic effects, related to the carbon atoms, occuring during the diffusion of carbon dioxide between two phases. Photosynthesis experiments performed with algae suspensions (Euglena gracilis) or aerial leaves (Saccharum officinale, Lycopersicum esculantum, Platanus orientalis, Sinapis alba...) have led to determine an Isotopic Discrimination Factor between 12 C and 13 C very close to 1. The method can be applied to the study of isotopic effects in enzymatic reactions involving CO 2 [fr

  15. Stable isotope and modelling evidence for CO2 as a driver of glacial–interglacial vegetation shifts in southern Africa

    Directory of Open Access Journals (Sweden)

    F. J. Bragg

    2013-03-01

    Full Text Available Atmospheric CO2 concentration is hypothesized to influence vegetation distribution via tree–grass competition, with higher CO2 concentrations favouring trees. The stable carbon isotope (δ13C signature of vegetation is influenced by the relative importance of C4 plants (including most tropical grasses and C3 plants (including nearly all trees, and the degree of stomatal closure – a response to aridity – in C3 plants. Compound-specific δ13C analyses of leaf-wax biomarkers in sediment cores of an offshore South Atlantic transect are used here as a record of vegetation changes in subequatorial Africa. These data suggest a large increase in C3 relative to C4 plant dominance after the Last Glacial Maximum. Using a process-based biogeography model that explicitly simulates 13C discrimination, it is shown that precipitation and temperature changes cannot explain the observed shift in δ13C values. The physiological effect of increasing CO2 concentration is decisive, altering the C3/C4 balance and bringing the simulated and observed δ13C values into line. It is concluded that CO2 concentration itself was a key agent of vegetation change in tropical southern Africa during the last glacial–interglacial transition. Two additional inferences follow. First, long-term variations in terrestrial δ13Cvalues are not simply a proxy for regional rainfall, as has sometimes been assumed. Although precipitation and temperature changes have had major effects on vegetation in many regions of the world during the period between the Last Glacial Maximum and recent times, CO2 effects must also be taken into account, especially when reconstructing changes in climate between glacial and interglacial states. Second, rising CO2 concentration today is likely to be influencing tree–grass competition in a similar way, and thus contributing to the "woody thickening" observed in savannas worldwide. This second inference points to the importance of experiments to

  16. Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

    International Nuclear Information System (INIS)

    Hansen, P.E.; Langgard, M.; Bolvig, S.

    1998-01-01

    Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

  17. Isotope effect on charge transfer in collisions of H with He^+ and He2+

    Science.gov (United States)

    Vaeck, N.; Loreau, J.; Ryabchenko, S.

    2011-05-01

    Data on charge exchange mechanism between ions and neutral atoms or molecules are central to the interpretation of measurements of the chemical composition in several astrophysical environments. In this work, we study the charge transfer process in collisions of H with He^+ or He2+ ions at energies between 0.1 and 200 eV/amu. To calculate the cross section for these reactions, we use a quantal method which consists in a combination of ab initio and wave packet propagat ion methods, and compare our results with the use of the semi-classical eikonal method. We consider in particular the isotope effect that arises when hydrogen is replaced by deuterium or tritium. Indeed, it was demonstrated using semi-classical methods that the isotope effect could be important at energies as high as 100 eV/amu. This large isotopic effect would contradict the commun knowledge that hydrogen, deuterium and tritium could be interchangeable in charge exchange processes above 1 eV/amu.

  18. Isotopic Effects on Stereodynamics of the C+ + H2 → CH+ + H Reaction

    Science.gov (United States)

    Guo, Lu; Yang, Yun-Fan; Fan, Xiao-Xing; Ma, Feng-Cai; Li, Yong-Qing

    2017-05-01

    The effects of isotope substitution on stereodynamic properties for the reactions {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T have been studied applying a quasi classical trajectory method occurring on the new ground state {{C H}}2+ potential energy surface [J. Chem. Phys. 142 (2015) 124302]. In the center of mass coordinates applying the quasi classical trajectory method to investigate the orientation and the alignment of the product molecule. Differential cross section and three angle distribution functions P(θr), P(ϕr), P( {θ }r,{φ }r ) on the potential energy surface that fixed the collision energy with a value is 40 kcal/mol have been studied. The isotope effect becomes more and more important with the reagent molecules H 2 changing into HD and HT. P({θ }r,{φ }r) as the joint probability density function of both polar angles θ r and ϕ r , which can illustrate more detailed dynamics information. The isotope effect is obvious influence on the properties of stereodynamics in the reactions of {C}++{H}2/{H D}/{H T}\\to {{C H}}++H/D/T. Supported by the National Natural Science Foundation of China under Grant Nos. 11474141, 11274149, 11544015, the Program for Liaoning Excellent Talents in University under Grant No. LJQ2015040, and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2014-1685)

  19. Evaluation of the effects of microscale chemical and isotopic ...

    Indian Academy of Sciences (India)

    reconstruction. Conventional Sr/Ca and δ18O paleothermometers are, however, based on the analysis of the mixture of the COC and SFS, and thus may be significantly ... the effects may yield significant or serious errors in paleotemperature reconstruction. 1. ..... tal geochemistry and paleoenvironmental reconstruction;.

  20. The genetic link between the Azores Archipelago and the Southern Azores Seamount Chain (SASC): The elemental, isotopic and chronological evidences

    Science.gov (United States)

    Ribeiro, Luisa Pinto; Martins, Sofia; Hildenbrand, Anthony; Madureira, Pedro; Mata, João

    2017-12-01

    New geochemical, isotopic (Sr-Nd-Hf-Pb) and K-Ar data, are presented here on samples from the Southern Azores Seamount Chain (SASC) located south of the Azores Plateau. The SASC also includes the Great Meteor, Small Meteor and Closs seamounts, morphologically connected by a saddle at - 4100 m deep. We conclude that the SASC are characterized by a narrow isotopic variability that falls within the Azores isotopic field. Although each seamount has its own isotopic signature, their mantle source must comprise four local mantle end-members, three of which are common to the Azores, e.g. Plato isotopic signature results from the mixing between HIMU and N-MORB while Great Meteor signature results from this mix with the Azores Common Component (AzCC). A fourth end-member with high 208Pb/204Pb and decoupled Th/U ratios (Δ8/4 up to 59.2) is identified on Great Meteor northern flank. New K-Ar ages on Plato (33.4 ± 0.5 Ma) and Small Hyeres (31.6 ± 0.4 Ma) show nearly coeval volcanism, which is contemporaneous with the E-MORBs erupted at the MAR, drilled on oceanic crust with 30-34 Ma (DSDP82). This study endorses the genetic link between the Azores Archipelago and the SASC to the long-term activity of the Azores plume and the large-scale ridge-hotspot interaction, contributing to better constrain the temporal-spatial evolution of this region of the North Atlantic.

  1. A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

    Science.gov (United States)

    Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

    2014-12-01

    Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

  2. Kinetic α-deuterium isotope effect as a probe of transition state structure and reaction mechanism in nucleoside hydrolysis

    International Nuclear Information System (INIS)

    Stein, R.L.

    1978-01-01

    Theoretical equilibrium α-deuterium isotope effects were calculated for systems modeling nucleoside and glycoside hydrolyses using a computer program (Burton, G.W., Sims, L.B., Wilson, J.C., and Fry, A.J., J. Amer. Chem. Soc., 99, 3374(1977)) which computes isotope effects directly from the expression of Biegeleisen and Mayer (Biegeleisen, J. and Mayer, M.G., J. Chem. Phys., 17, 675(1949)). For nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate, KH/KD = 1.21 to 1.25; while for nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate KH/KD = 1.15 to 1.19. The models used in the calculations were generated systematically and involved a minimum of subjectivity in the selection of molecular parameters. The isotope effects calculated formed the basis for the interpretation of experimental kinetic α-deuterium isotope effects for nucleoside and glycoside hydrolysis

  3. Effectiveness of Evidence-Based Asthma Interventions.

    Science.gov (United States)

    Kennedy, Suzanne; Bailey, Ryan; Jaffee, Katy; Markus, Anne; Gerstein, Maya; Stevens, David M; Lesch, Julie Kennedy; Malveaux, Floyd J; Mitchell, Herman

    2017-06-01

    Researchers often struggle with the gap between efficacy and effectiveness in clinical research. To bridge this gap, the Community Healthcare for Asthma Management and Prevention of Symptoms (CHAMPS) study adapted an efficacious, randomized controlled trial that resulted in evidence-based asthma interventions in community health centers. Children (aged 5-12 years; N = 590) with moderate to severe asthma were enrolled from 3 intervention and 3 geographically/capacity-matched control sites in high-risk, low-income communities located in Arizona, Michigan, and Puerto Rico. The asthma intervention was tailored to the participant's allergen sensitivity and exposure, and it comprised 4 visits over the course of 1 year. Study visits were documented and monitored prospectively via electronic data capture. Asthma symptoms and health care utilization were evaluated at baseline, and at 6 and 12 months. A total of 314 intervention children and 276 control children were enrolled in the study. Allergen sensitivity testing (96%) and home environmental assessments (89%) were performed on the majority of intervention children. Overall study activity completion (eg, intervention visits, clinical assessments) was 70%. Overall and individual site participant symptom days in the previous 4 weeks were significantly reduced compared with control findings (control, change of -2.28; intervention, change of -3.27; difference, -0.99; P asthma in these high-need populations. Copyright © 2017 by the American Academy of Pediatrics.

  4. Millennial-scale isotope records from a wide-ranging predator show evidence of recent human impact to oceanic food webs.

    Science.gov (United States)

    Wiley, Anne E; Ostrom, Peggy H; Welch, Andreanna J; Fleischer, Robert C; Gandhi, Hasand; Southon, John R; Stafford, Thomas W; Penniman, Jay F; Hu, Darcy; Duvall, Fern P; James, Helen F

    2013-05-28

    Human exploitation of marine ecosystems is more recent in oceanic than near shore regions, yet our understanding of human impacts on oceanic food webs is comparatively poor. Few records of species that live beyond the continental shelves date back more than 60 y, and the sheer size of oceanic regions makes their food webs difficult to study, even in modern times. Here, we use stable carbon and nitrogen isotopes to study the foraging history of a generalist, oceanic predator, the Hawaiian petrel (Pterodroma sandwichensis), which ranges broadly in the Pacific from the equator to near the Aleutian Islands. Our isotope records from modern and ancient, radiocarbon-dated bones provide evidence of over 3,000 y of dietary stasis followed by a decline of ca. 1.8‰ in δ(15)N over the past 100 y. Fishery-induced trophic decline is the most likely explanation for this sudden shift, which occurs in genetically distinct populations with disparate foraging locations. Our isotope records also show that coincident with the apparent decline in trophic level, foraging segregation among petrel populations decreased markedly. Because variation in the diet of generalist predators can reflect changing availability of their prey, a foraging shift in wide-ranging Hawaiian petrel populations suggests a relatively rapid change in the composition of oceanic food webs in the Northeast Pacific. Understanding and mitigating widespread shifts in prey availability may be a critical step in the conservation of endangered marine predators such as the Hawaiian petrel.

  5. The Pleistocene evolution of the East Antarctic Ice Sheet in the Prydz bay region: Stable isotopic evidence from ODP Site 1167

    Science.gov (United States)

    Theissen, K.M.; Dunbar, R.B.; Cooper, A. K.; Mucciarone, D.A.; Hoffmann, D.

    2003-01-01

    Ocean Drilling Program Leg 188, Prydz Bay, East Antarctica is part of a larger initiative to explore the Cenozoic history of the Antarctic Ice Sheet through direct drilling and sampling of the continental margins. In this paper, we present stable isotopic results from Ocean Drilling Program (ODP) Site 1167 located on the Prydz Channel Trough Mouth Fan (TMF), the first Antarctic TMF to be drilled. The foraminifer-based ??18O record is interpreted along with sedimentary and downhole logging evidence to reconstruct the Quaternary glacial history of Prydz Bay and the adjacent Lambert Glacier Amery Ice Shelf System (LGAISS). We report an electron spin resonance age date of 36. 9 ?? 3.3 ka at 0.45 m below sea floor and correlate suspected glacial-interglacial cycles with the global isotopic stratigraphy to improve the chronology for Site 1167. The ??18O record based on planktonic (Neogloboquadrina pachyderma (s.)) and limited benthic results (Globocassidulina crassa), indicates a trend of ice sheet expansion that was interrupted by a period of reduced ice volume and possibly warmer conditions during the early-mid-Pleistocene (0.9-1.38 Ma). An increase in ?? 18O values after ??? 900 ka appears to coincide with the mid-Pleistocene climate transition and the expansion of the northern hemisphere ice sheet. The ??18O record in the upper 50 m of the stratigraphic section indicates as few as three glacial-interglacial cycles, tentatively assigned as marine isotopic stages (MIS) 16-21, are preserved since the Brunhes/Matuyama paleomagnetic reversal (780 ka). This suggests that there is a large unconformity near the top of the section and/or that there may have been few extreme advances of the ice sheet since the mid-Pleistocene climate transition resulting in lowered sedimentation rates on the Prydz Channel TMF. The stable isotopic record from Site 1167 is one of the few available from the area south of the Antarctic Polar Front that has been linked with the global isotopic

  6. Laser assisted aerodynamic isotope separation

    International Nuclear Information System (INIS)

    Berg, H. van den

    1985-01-01

    It is shown that the efficiency of conventional aerodynamic isotope seperation can be improved by two orders of magnitude with the aid of a relatively weak cw infrared laser which is used to induce isotopically selective condensation. Overall isotope enrichment factors in excess of 2 are obtained as compared to about 1.02 in the conventional seperation. Sulphur isotopes in SF 6 as well as Silicon isotopes in SiF 4 and Bromine isotopes in CF 3 Br are seperated on a laboratory scale. Infrared vibrational predissociation by itself and in combination with isotopically selective condensation are also shown to be effective new ways of isotope separation. (orig.) [de

  7. Use of isotope effects to determine the chemical mechanism of oxidative decarboxylases: NADP malic enzyme and NADP isocitrate dehydrogenase

    International Nuclear Information System (INIS)

    Grisson, C.B.

    1985-01-01

    The chemical mechanism of the NADP-linked oxidative decarboxylases chicken liver malic enzyme and pig heart isocitrate dehydrogenase has been examined using carbon and deuterium isotope effects and their variation with pH, metal ions, and solution viscosity. The following 13 C isotope effects on V/K for malate are observed with the stated metal ion at pH 8.0 and 25 0 C: Mg 2+ , 1.0336; Mn 2+ , 1.0365; Cd 2+ , 1.0366; Zn 2+ , 1.03373; Co 2+ , 1.0283; and Ni 2+ , 1.025. The 13 C isotope effect on nonenzymatic decarboxylation of dibasic oxalacetate at 25 0 C and the stated metal ion is : Mg 2+ , 1.0489; Mn 2+ , 1.0505; Ni 2+ , 1.044; Cd 2+ , 1.0492; Zn 2+ , 1.0504; and Co 2+ , 1.0480. By quantitating the partitioning of the 2-ketocarboxylic acid reaction intermediate between reverse hydride transfer and decarboxylation, it is possible to solve for the intrinsic isotope effects in both reactions. With malic enzyme activated by Mg 2+ , the partitioning ratio of oxalacetate between pyruvate and malate formation is 0.47. This gives an intrinsic deuterium and 13 C isotope effect of 5.6 and 1.0493, respectively. The 13 C isotope effect for the Mg 2+ catalyzed nonenzymatic decarboxylation of oxalacetate is 1.0489, thereby suggesting a similarity of transition states between the enzymatic and nonenzymatic processes. The observed 13 C primary isotope effect for isocitrate in the isocitrate dehydrogenase reaction is obscured by the stickiness of isocitrate at neutral pH. At low pH, the external commitment is eliminated and the observed 13 C isotope effect increases to a limiting value of 1.0353. The pK of the pH dependence of 13 (V/K) is 4.7

  8. Determination of ionization potential of atomic gadolinium and its isotope effect. Analysis of unperturbed Rydberg series

    Energy Technology Data Exchange (ETDEWEB)

    Miyabe, Masabumi; Ohba, Masaki; Wakaida, Ikuo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-10-01

    Autoionizing Rydberg series converging to six states (0, 261.841, 633.273, 3082.011, 3427.274, 3444.235 cm{sup -1}) of Gd ion have been observed by using three-color three-step photoionization via ten different 2nd-step levels of J=0 or 1. While the perturbations with interlopers become significant in the region of n=30-35 for most of the observed series, long and well-defined series structures appeared in higher energy region. From an analysis of such unperturbed structures, the first ionization potential of Gd atom was estimated to be 49601.45 (30) cm{sup -1}. This is in good agreement with the previous value, but the accuracy is improved by about one order of magnitude. In addition, isotope effect on the ionization potential was also determined by isotope shifts of some Rydberg series. (author)

  9. Sensitized charge carrier injection into organic crystals studied by isotope effects in weak magnetic fields

    International Nuclear Information System (INIS)

    Bube, W.; Michel-Beyerle, M.E.; Haberkorn, R.; Steffens, E.

    1977-01-01

    The magnetic field (H approximately 50 Oe) dependence of the rhodamine sensitized triplet exciton density in anthracene crystals is influenced by isotopic substitution. This confirms the hyperfine interaction as mechanism explaining the change of the spin multiplicity in the initially formed singlet state of the radical pair. The isotope effect occurs in the sensitizing dye ( 14 N/ 15 N) rather than at the molecular site of the injected charge within the crystal. This can be understood in terms of the high hopping frequency of the charge carriers as compared to the time constant of the hyperfine induced singlet-triplet transition. Since the dye molecules adsorb in an oriented fashion, the angular dependence of the magnetic field modulation of the triplet exciton density can be interpreted without assuming any additional interactions. (Auth.)

  10. Communication: Isotopic effects on tunneling motions in the water trimer

    Energy Technology Data Exchange (ETDEWEB)

    Videla, Pablo E. [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Rossky, Peter J. [Department of Chemistry, Rice University, Houston, Texas 77251-1892 (United States); Laria, D., E-mail: dhlaria@cnea.gov.ar [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica, Avenida Libertador 8250, 1429 Buenos Aires (Argentina)

    2016-02-14

    We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H{sub 2}O]{sub 3} and [D{sub 2}O]{sub 3}, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H{sub 2}O]{sub 3} than in [D{sub 2}O]{sub 3}. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments.

  11. Geochemical and isotopic evidence on the recharge and circulation of geothermal water in the Tangshan Geothermal System near Nanjing, China: implications for sustainable development

    Science.gov (United States)

    Lu, Lianghua; Pang, Zhonghe; Kong, Yanlong; Guo, Qi; Wang, Yingchun; Xu, Chenghua; Gu, Wen; Zhou, Lingling; Yu, Dandan

    2018-01-01

    Geothermal resources are practical and competitive clean-energy alternatives to fossil fuels, and study on the recharge sources of geothermal water supports its sustainable exploitation. In order to provide evidence on the recharge source of water and circulation dynamics of the Tangshan Geothermal System (TGS) near Nanjing (China), a comprehensive investigation was carried out using multiple chemical and isotopic tracers (δ2H, δ18O, δ34S, 87Sr/86Sr, δ13C, 14C and 3H). The results confirm that a local (rather than regional) recharge source feeds the system from the exposed Cambrian and Ordovician carbonate rocks area on the upper part of Tangshan Mountain. The reservoir temperature up to 87 °C, obtained using empirical as well as theoretical chemical geothermometers, requires a groundwater circulation depth of around 2.5 km. The temperature of the geothermal water is lowered during upwelling as a consequence of mixing with shallow cold water up to a 63% dilution. The corrected 14C age shows that the geothermal water travels at a very slow pace (millennial scale) and has a low circulation rate, allowing sufficient time for the water to become heated in the system. This study has provided key information on the genesis of TGS and the results are instructive to the effective management of the geothermal resources. Further confirmation and even prediction associated with the sustainability of the system could be achieved through continuous monitoring and modeling of the responses of the karstic geothermal reservoir to hot-water mining.

  12. Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Bruce S. [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Lollar, Barbara Sherwood [Earth Sciences Department, University of Toronto, 22 Russell Street, Toronto, ON M5S 3B1 (Canada); Passeport, Elodie [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Chemical Engineering and Applied Chemistry Department, University of Toronto, 200 College Street, Toronto, ON M5S 3E5 (Canada); Sleep, Brent E., E-mail: sleep@ecf.utoronto.ca [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada)

    2016-04-15

    Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C{sub 0}), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D{sub mech}/D{sub eff}). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C{sub 0}/MDL ratios of 50 or higher. Much larger C{sub 0}/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D{sub mech}/D{sub eff} is

  13. Fossil Mice and Rats Show Isotopic Evidence of Niche Partitioning and Change in Dental Ecomorphology Related to Dietary Shift in Late Miocene of Pakistan

    Science.gov (United States)

    Kimura, Yuri; Jacobs, Louis L.; Cerling, Thure E.; Uno, Kevin T.; Ferguson, Kurt M.; Flynn, Lawrence J.; Patnaik, Rajeev

    2013-01-01

    Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ13C) with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ13C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible. PMID:23936324

  14. Fossil mice and rats show isotopic evidence of niche partitioning and change in dental ecomorphology related to dietary shift in Late Miocene of Pakistan.

    Directory of Open Access Journals (Sweden)

    Yuri Kimura

    Full Text Available Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ(13C with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ(13C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible.

  15. Measurement of the isotope effect of the diffusion of silver and gold in gold and of silver in silver-gold alloys

    International Nuclear Information System (INIS)

    Wolter, D.

    1974-01-01

    The silver isotopes Ag 105 and Agsup(110m) and the gold isotopes Au 195 and Au 199 were used for isotope effect measurements. The isotope effect of the gold self-diffusion was measured on four monocrystals samples at about 850 0 C, that of silver in gold monocrystals at five different temperatures between 731 0 C and 1050 0 C. Furthermore, the isotope effect for silver at 904 0 C was measured on seven silver-gold alloys of varying silver concentration. The correlation factor was determined from the measurements. (HPOE/LH) [de

  16. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  17. The isotopic contamination in electromagnetic isotope separators

    International Nuclear Information System (INIS)

    Cassignol, Ch.

    1959-01-01

    In the early years of isotope separation, and in particular electromagnetic isotope separation, needs for rapid results have conducted to empiric research. This paper describes fundamental research on the electromagnetic isotope separation to a better understanding of isotope separators as well as improving the performances. Focus has been made on the study of the principle of isotope contamination and the remedial action on the separator to improve the isotope separation ratio. In a first part, the author come back to the functioning of an electromagnetic separator and generalities on isotope contamination. Secondly, it describes the two stages separation method with two dispersive apparatus, an electromagnetic separation stage followed by an electrostatic separation stage, both separated by a diaphragm. The specifications of the electrostatic stage are given and its different settings and their consequences on isotope separation are investigated. In a third part, mechanisms and contamination factors in the isotope separation are discussed: natural isotope contamination, contamination by rebounding on the collector, contamination because of a low resolution, contamination by chromatism and diffusion effect, breakdown of condenser voltage. Analysis of experimental results shows the diffusion as the most important contamination factor in electromagnetic isotope separation. As contamination factors are dependent on geometric parameters, sector angle, radius of curvature in the magnetic field and clearance height are discussed in a fourth part. The better understanding of the mechanism of the different contamination factors and the study of influential parameters as pressure and geometric parameters lead to define a global scheme of isotope contamination and determinate optima separator design and experimental parameters. Finally, the global scheme of isotope contamination and hypothesis on optima specifications and experimental parameters has been checked during a

  18. Sources and fate of mercury pollution in Almadén mining district (Spain): Evidences from mercury isotopic compositions in sediments and lichens.

    Science.gov (United States)

    Jiménez-Moreno, María; Barre, Julien P G; Perrot, Vincent; Bérail, Sylvain; Rodríguez Martín-Doimeadios, Rosa C; Amouroux, David

    2016-03-01

    Variations in mercury (Hg) isotopic compositions have been scarcely investigated until now in the Almadén mining district (Spain), which is one of the most impacted Hg areas worldwide. In this work, we explore and compare Hg isotopic signatures in sediments and lichens from Almadén mining district and its surroundings in order to identify and trace Hg aquatic and atmospheric contamination sources. No statistically significant mass independent fractionation was observed in sediments, while negative Δ(201)Hg values from -0.12 to -0.21‰ (2SD = 0.06‰) were found in lichens. A large range of δ(202)Hg values were reported in sediments, from -1.86 ± 0.21‰ in La Serena Reservoir sites far away from the pollution sources to δ(202)Hg values close to zero in sediments directly influenced by Almadén mining district, whereas lichens presented δ(202)Hg values from -1.95 to -0.40‰ (2SD = 0.15‰). A dilution or mixing trend in Hg isotope signatures versus the distance to the mine was found in sediments along the Valdeazogues River-La Serena Reservoir system and in lichens. This suggests that Hg isotope fingerprints in these samples are providing a direct assessment of Hg inputs and exposure from the mining district, and potential information on diffuse atmospheric contamination and/or geochemical alteration processes in less contaminated sites over the entire hydrosystem. This study confirms the applicability of Hg isotope signatures in lichens and sediments as an effective and complementary tool for tracing aquatic and atmospheric Hg contamination sources and a better constraint of the spatial and temporal fate of Hg released by recent or ancient mining activities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

    Science.gov (United States)

    Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

    2017-12-01

    Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

  20. Sugar cane consumption on Rapanui (Easter Island) and the indicence of caries : evidence from stable isotope values of human bone

    International Nuclear Information System (INIS)

    Leach, B.F.; Quinn, C.J.; Seelenfreund, A.

    2017-01-01

    Pre-European people on Rapanui are known to have had a high rate of dental caries. One proposed explanation for this is that the people consumed a considerable amount of sugar cane, as a thirst quencher, since fresh water is scarce on the island. Human bone samples were analysed by isotope analysis to see if this explanation could be sustained. Results for three isotopes δ 13 C, δ 15 N and δ 34 S were then used in a stochastic model to estimate the proportions of five main food types in the diet of these people. This indicated that daily consumption of dry raw sugar cane was only about 32 to 42 g per day. This is very low and sugar cane consumption is therefore unlikely to be the only cause of the high rate of dental caries. (author).

  1. Distribution of uranium, thorium, and isotopic composition of uranium in soil samples of south Serbia: Evidence of depleted uranium

    Directory of Open Access Journals (Sweden)

    Sahoo Sarata Kumar

    2004-01-01

    Full Text Available Inductively coupled plasma mass spectrometry and thermal ionization mass spectrom - etry were used to measure concentration of uranium and thorium as well as isotopic composition of uranium respectively in soil samples collected around south Serbia. An analytical method was established for a routine sample preparation procedure for uranium and thorium. Uranium was chemically separated and purified from soil samples by anion exchange resin and UTEVA extraction chromatography and its isotopic composition was measured using a thermal ionization mass spectrometry. There was a little deviation of U/Th ratio from the average values in some soil samples. Presence of 236U as well as depleted uranium was observed in 235U/238U ratio measurement in the same soil sample.

  2. The parent body controls on cosmic spherule texture: Evidence from the oxygen isotopic compositions of large micrometeorites

    Science.gov (United States)

    van Ginneken, M.; Gattacceca, J.; Rochette, P.; Sonzogni, C.; Alexandre, A.; Vidal, V.; Genge, M. J.

    2017-09-01

    High-precision oxygen isotopic compositions of eighteen large cosmic spherules (>500 μm diameter) from the Atacama Desert, Chile, were determined using IR-laser fluorination - Isotope Ratio Mass spectrometry. The four discrete isotopic groups defined in a previous study on cosmic spherules from the Transantarctic Mountains (Suavet et al., 2010) were identified, confirming their global distribution. Approximately 50% of the studied cosmic spherules are related to carbonaceous chondrites, 38% to ordinary chondrites and 12% to unknown parent bodies. Approximately 90% of barred olivine (BO) cosmic spherules show oxygen isotopic compositions suggesting they are related to carbonaceous chondrites. Similarly, ∼90% porphyritic olivine (Po) cosmic spherules are related to ordinary chondrites and none can be unambiguously related to carbonaceous chondrites. Other textures are related to all potential parent bodies. The data suggests that the textures of cosmic spherules are mainly controlled by the nature of the precursor rather than by the atmospheric entry parameters. We propose that the Po texture may essentially be formed from a coarse-grained precursor having an ordinary chondritic mineralogy and chemistry. Coarse-grained precursors related to carbonaceous chondrites (i.e. chondrules) are likely to either survive atmospheric entry heating or form V-type cosmic spherules. Due to the limited number of submicron nucleation sites after total melting, ordinary chondrite-related coarse-grained precursors that suffer higher peak temperatures will preferentially form cryptocrystalline (Cc) textures instead of BO textures. Conversely, the BO textures would be mostly related to the fine-grained matrices of carbonaceous chondrites due to the wide range of melting temperatures of their constituent mineral phases, allowing the preservation of submicron nucleation sites. Independently of the nature of the precursors, increasing peak temperatures form glassy textures.

  3. Behaviour of zircon in high-grade metamorphic rocks: evidence from Hf isotopes, trace elements and textural studies

    Czech Academy of Sciences Publication Activity Database

    Sláma, Jiří; Košler, J.; Pedersen, R. B.

    2007-01-01

    Roč. 154, č. 3 (2007), s. 335-356 ISSN 0010-7999 Grant - others:Grant Agency of the Charles University(CZ) 264/2005/B-GEO Institutional research plan: CEZ:AV0Z30130516 Keywords : Hf isotopes * zircon * granulite * U-Pb dating * laser ablation * ICP-MS * garnet * decompression * metamorphic reaction Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.216, year: 2007

  4. Trace-element and Sr-Nd isotopic evidence for the origin of the Sardinian fluorite mineralization (Italy)

    International Nuclear Information System (INIS)

    Castorina, F.; Masi, U.; Padalino, G.; Palomba, M.

    2008-01-01

    The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus 87 Sr/ 86 Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial ε Nd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial ε Nd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids

  5. Isotopic Composition of Atmospheric Mercury in China: New Evidence for Sources and Transformation Processes in Air and in Vegetation.

    Science.gov (United States)

    Yu, Ben; Fu, Xuewu; Yin, Runsheng; Zhang, Hui; Wang, Xun; Lin, Che-Jen; Wu, Chuansheng; Zhang, Yiping; He, Nannan; Fu, Pingqing; Wang, Zifa; Shang, Lihai; Sommar, Jonas; Sonke, Jeroen E; Maurice, Laurence; Guinot, Benjamin; Feng, Xinbin

    2016-09-06

    The isotopic composition of atmospheric total gaseous mercury (TGM) and particle-bound mercury (PBM) and mercury (Hg) in litterfall samples have been determined at urban/industrialized and rural sites distributed over mainland China for identifying Hg sources and transformation processes. TGM and PBM near anthropogenic emission sources display negative δ(202)Hg and near-zero Δ(199)Hg in contrast to relatively positive δ(202)Hg and negative Δ(199)Hg observed in remote regions, suggesting that different sources and atmospheric processes force the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) in the air samples. Both MDF and MIF occur during the uptake of atmospheric Hg by plants, resulting in negative δ(202)Hg and Δ(199)Hg observed in litter-bound Hg. The linear regression resulting from the scatter plot relating the δ(202)Hg to Δ(199)Hg data in the TGM samples indicates distinct anthropogenic or natural influences at the three study sites. A similar trend was also observed for Hg accumulated in broadleaved deciduous forest foliage grown in areas influenced by anthropogenic emissions. The relatively negative MIF in litter-bound Hg compared to TGM is likely a result of the photochemical reactions of Hg(2+) in foliage. This study demonstrates the diagnostic stable Hg isotopic composition characteristics for separating atmospheric Hg of different source origins in China and provides the isotopic fractionation clues for the study of Hg bioaccumulation.

  6. Identification of sources and causes of leakage on a zoned earth dam in northern Taiwan: Hydrological and isotopic evidence

    International Nuclear Information System (INIS)

    Peng, T.-R.; Wang, C.-H.

    2008-01-01

    Seepage through an earth dam body must be regulated as a well-planned process, if it is not properly managed, the abnormal seepage may cause dam failure. This study employed stable isotopic and statistical methods to identify the source and cause of an abnormal leakage on the zoned earth dam of the Xin-Shan reservoir located in northern Taiwan. Water samples from the dam area over a 2-a period were collected and analyzed for their stable O and H isotope compositions. In addition, a 4-a period of hydrological data, including rainfall, reservoir level, well level, seepage of filter drainage and leakage, were statistically analyzed with a stepwise multiple regression approach. Both the stable isotopic and hydrological results indicate that the abnormal leakage on the dam shell comes from the filter drainage in the dam. The reason for abnormal leakage is due to unexpected and significant precipitation-sourced water flowing into the dam's body. The dam filter fails to drain out the incoming water sufficiently, thus generating the abnormal seepage. In addition, the defect in the dam filter may also cause the drainage filter to drain off reservoir seepage inadequately. Therefore, it is suggested that checking the filter function and preventing excessive precipitation-sourced water from flowing into the dam are the two top priorities for the follow-up remedial strategy of the dam

  7. Lead isotope evidence for recent uranium mobility in geological formations of Brazil: implications for radioactive waste disposal

    International Nuclear Information System (INIS)

    Iyer, S.S.; Babinski, M.; Marinho, M.M.; Barbosa, J.S.F.; Sato, I.M.; Salvador, V.L.

    1999-01-01

    Lead-lead isotope data from whole rock samples are used to investigate the recent (last few million years) mobility of U and Th. The method is based on the comparison of the calculated present day U and Th concentrations required to yield the Pb isotope composition in the samples with the actual present day concentrations of U and Th obtained by direct measurement. The geological formations studied include the Neoproterozoic carbonate sediments of the Bambui Group, Archean/Paleoproterozoic granite-greenstone terrain of the Contendas-Mirante Complex and a Proterozoic ortho-gneisses hosting U deposit in Lagoa Real. All these formations are in the Sao Francisco Craton, Brazil. The data show high U mobility in the carbonate sediments and in the deformed ortho-gneisses set in a ductile shear zone. Infiltration of groundwater through fault zones seems to have facilitated the U mobility. The Pb isotope approach is a useful technique complementing U-series disequilibrium studies and may be included for site characterization studies for radioactive waste disposal. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  8. Spatial variations in food web structures with alternative stable states: evidence from stable isotope analysis in a large eutrophic lake

    Science.gov (United States)

    Li, Yunkai; Zhang, Yuying; Xu, Jun; Zhang, Shuo

    2017-05-01

    Food web structures are well known to vary widely among ecosystems. Moreover, many food web studies of lakes have generally attempted to characterize the overall food web structure and have largely ignored internal spatial and environmental variations. In this study, we hypothesize that there is a high degree of spatial heterogeneity within an ecosystem and such heterogeneity may lead to strong variations in environmental conditions and resource availability, in turn resulting in different trophic pathways. Stable carbon and nitrogen isotopes were employed for the whole food web to describe the structure of the food web in different sub-basins within Taihu Lake. This lake is a large eutrophic freshwater lake that has been intensively managed and highly influenced by human activities for more than 50 years. The results show significant isotopic differences between basins with different environmental characteristics. Such differences likely result from isotopic baseline differences combining with a shift in food web structure. Both are related to local spatial heterogeneity in nutrient loading in waters. Such variation should be explicitly considered in future food web studies and ecosystem-based management in this lake ecosystem.

  9. The effect of natural weathering on the chemical and isotopic composition of biotites

    International Nuclear Information System (INIS)

    Clauer, N.; Bonnot-Courtois, C.

    1982-01-01

    The effect of progressive natural weathering on the isotopic (Rb-Sr, K-Ar, deltaD, delta 18 O) and chemical (REE, H 2 O + ) compositions of biotite has been studied on a suite of migmatitic biotites from the Chad Republic. During the early stages of weathering the Rb-Sr system is strongly affected, the hydrogen and oxygen isotope compositions change markedly, the minerals are depleted in light REE, the water content increases by a factor of two, and the K-Ar system is relatively little disturbed. During intensive weathering the K-Ar system is more strongly disturbed than the Rb-Sr system. Most of the isotopic and chemical modifications take place under nonequilibrium conditions and occur before newly formed kaolinite and/or smectite can be detected. These observations suggest that (a) 'protominerals' may form within the biotite structure during the initial period of weathering, and (b) only when chemical equilibrium is approached in the weathering profile are new minerals able to form. (author)

  10. Stable isotope canopy effects for sympatric monkeys at Tai Forest, Cote d'Ivoire.

    Science.gov (United States)

    Krigbaum, John; Berger, Michael H; Daegling, David J; McGraw, W Scott

    2013-08-23

    This study tests the hypothesis that vertical habitat preferences of different monkey species inhabiting closed canopy rainforest are reflected in oxygen isotopes. We sampled bone from seven sympatric cercopithecid species in the Taï forest, Côte d'Ivoire, where long-term study has established taxon-specific patterns of habitat use and diet. Modern rib samples (n = 34) were examined for oxygen (δ(18)Oap) and carbon (δ(13)Cap) from bone apatite ('bioapatite'), and carbon (δ(13)Cco) and nitrogen (δ(15)Nco) from bone collagen. Results are consistent for C3 feeders in a closed canopy habitat. Low irradiance and evapotranspiration, coupled with high relative humidity and recycled CO2 in forest understory, contribute to observed isotopic variability. Both δ(13)Cco and δ(13)Cap results reflect diet; however, δ(13)C values are not correlated with species preference for canopy height. By contrast, δ(18)Oap results are correlated with mean observed height and show significant vertical partitioning between taxa feeding at ground, lower and upper canopy levels. This oxygen isotope canopy effect has important palaeobiological implications for reconstructing vertical partitioning among sympatric primates and other species in tropical forests.

  11. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    International Nuclear Information System (INIS)

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

    1989-01-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  12. Geochemical and isotopic evidence for palaeo-seawater intrusion into the south coast aquifer of Laizhou Bay, China

    International Nuclear Information System (INIS)

    Han Dongmei; Kohfahl, Claus; Song, Xianfang; Xiao Guoqiang; Yang Jilong

    2011-01-01

    Highlights: → Hydrochemistry, multi-isotopes, and hydraulic data were used to study saltwater intrusion. → Salt sources and their contributions to the salinity distribution are identified. → Groundwater age and mixing behavior are estimated. → Hydrogeochemical evolution of different types of groundwater is determined. → Multi-approach study can improve the understanding of reactive transport processes. - Abstract: This research aims to improve the current knowledge of groundwater salinisation processes in coastal aquifers using combined hydrochemical and isotopic parameters and inverse hydrochemical modelling. Field investigations were conducted in Laizhou Bay, which is the area most seriously affected by seawater intrusion in north China. During three sampling campaigns along a vertical transect in the Changyi-Liutuan area, 95 ground- and surface-water samples were collected for major ion and isotope analysis ( 2 H/ 18 O, 3 H, 14 C, 34 S). The groundwater changes along the general flowpath towards the coast from fresh ( 100 g/L). Molar Cl/Br ratios are close to those of seawater in almost all groundwater samples, indicating that brines and deep seawater evolved from different events of palaeo-seawater intrusion. Depleted isotopic signatures of brines and deep saline water point to a former, initially depleted seawater reservoir due to runoff dilution. Tritium and 14 C activities in deep saline water below confining units indicate isolation from modern precipitation and significant residence times. Brine water shows a wide range of 3 H and 14 C ages due to the complex conditions of mixing without isolation from modern groundwater. Sulphur-34 isotope ratios support seawater intrusion as a possible salt origin, although this parameter does not exclude gypsum dissolution. The combined use of Cl and 18 O yields four different end-members of groundwater, and three different mixing scenarios were identified explaining the hydrochemical composition of

  13. Evidence of the exploitation of marine resource by the terrestrial insect Scapteriscus didactylus through stable isotope analyzes of its cuticle

    Directory of Open Access Journals (Sweden)

    Lelarge Caroline

    2006-05-01

    Full Text Available Abstract Background About 4 × 105 eggs in more than 5000 marine turtle nests are deposited every year on a 3.6 km long beach in French Guiana (South America. The dry biomass of eggs is estimated to be 5 × 103 kg, yet only 25% of this organic matter will return to the ocean in the form of hatchlings. Such amounts of organic matter are supposed to drive the functioning of the beach ecosystem. Previous studies have shown that egg predators and detritivorous organisms dominate the trophic relationships and the dynamics of the system. The role of a terrestrial insect Scapteriscus didactylus (Latreille, which damages up to 40% of the eggs of the marine turtle (Dermochelys coriacea, was unexpected. However it was impossible from direct observations to prove that the mole cricket consumed a significant amount of these eggs. Therefore, the precise place of the mole cricket in the nitrogen and carbon cycles of the beach ecosystem could not be determined. In order to answer this question, we looked for a marine signature of carbon and nitrogen source metabolized by the mole cricket. Results This study estimated the individual variability of δ13C and δ15N in the cuticle of Scapteriscus didactylus. The isotopic signature was compared between individuals collected at two sites: a village where mole crickets fed on human food scraps and the nearby Awala-Yalimapo beach, where food availability depends seasonally on the nesting sea turtles. The mole crickets collected near the habitations garbage showed no significant variations in the stable isotopic signature, within-and between age groups. On the contrary, isotopic values shifted from a signature of a terrestrial herbivorous diet in the mole crickets during early developmental stages, to isotopic values in adults in accordance with the exploitation of marine animal resources. Conclusion The heterogeneity of individual signatures during the year is due to a selective exploitation of the food sources

  14. Geochemical and isotopic evidence for palaeo-seawater intrusion into the south coast aquifer of Laizhou Bay, China

    Energy Technology Data Exchange (ETDEWEB)

    Han Dongmei [Key Laboratory of Water Cycle and Related Land Surface Processes, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101 (China); Kohfahl, Claus [Instituto Geologico y Minero de Espana, Plaza de Espana, 41013 Seville (Spain); Song, Xianfang, E-mail: songxf@igsnrr.ac.cn [Key Laboratory of Water Cycle and Related Land Surface Processes, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101 (China); Xiao Guoqiang; Yang Jilong [Tianjin Institute of Geology and Mineral Resources, Tianjin 300170 (China)

    2011-05-15

    Highlights: > Hydrochemistry, multi-isotopes, and hydraulic data were used to study saltwater intrusion. > Salt sources and their contributions to the salinity distribution are identified. > Groundwater age and mixing behavior are estimated. > Hydrogeochemical evolution of different types of groundwater is determined. > Multi-approach study can improve the understanding of reactive transport processes. - Abstract: This research aims to improve the current knowledge of groundwater salinisation processes in coastal aquifers using combined hydrochemical and isotopic parameters and inverse hydrochemical modelling. Field investigations were conducted in Laizhou Bay, which is the area most seriously affected by seawater intrusion in north China. During three sampling campaigns along a vertical transect in the Changyi-Liutuan area, 95 ground- and surface-water samples were collected for major ion and isotope analysis ({sup 2}H/{sup 18}O, {sup 3}H, {sup 14}C, {sup 34}S). The groundwater changes along the general flowpath towards the coast from fresh (<1 g/L), brackish (1-10 g/L), saline (10-100 g/L) to brine water (>100 g/L). Molar Cl/Br ratios are close to those of seawater in almost all groundwater samples, indicating that brines and deep seawater evolved from different events of palaeo-seawater intrusion. Depleted isotopic signatures of brines and deep saline water point to a former, initially depleted seawater reservoir due to runoff dilution. Tritium and {sup 14}C activities in deep saline water below confining units indicate isolation from modern precipitation and significant residence times. Brine water shows a wide range of {sup 3}H and {sup 14}C ages due to the complex conditions of mixing without isolation from modern groundwater. Sulphur-34 isotope ratios support seawater intrusion as a possible salt origin, although this parameter does not exclude gypsum dissolution. The combined use of Cl and {sup 18}O yields four different end-members of groundwater, and

  15. Wildfire Activity Across the Triassic-Jurassic Boundary in the Polish Basin: Evidence from New Fossil Charcoal & Carbon-isotope Data

    Science.gov (United States)

    Pointer, R.; Belcher, C.; Hesselbo, S. P.; Hodbod, M.; Pieńkowski, G.

    2017-12-01

    New fossil charcoal abundance and carbon-isotope data from two sedimentary cores provide new evidence of extreme environmental conditions in the Polish Basin during the Latest Triassic to Earliest Jurassic. Sedimentary cores from the Polish Basin provide an excellent record of terrestrial environmental conditions across the Triassic-Jurassic Boundary, a time of climatic extremes. Previous work has shown that the marine realm was affected by a large perturbation to the carbon cycle across the Triassic-Jurassic Boundary (manifested by large negative and positive carbon-isotope excursions) and limited records of charcoal abundance and organic geochemistry have indicated important changes in fire regime in the coeval ecosystems. Here we present two new carbon-isotope records generated from fossil plant matter across the Triassic-Jurassic boundary, and present new charcoal records. The charcoal abundance data confirm that there was variation in wildfire activity during the Late Triassic-Early Jurassic in the Polish Basin. Peaks in the number of fossil charcoal fragments present occur in both sedimentary cores, and increases in fossil charcoal abundance are linked to wildfires, signalling a short-lived rise in wildfire activity. Fossil charcoal abundance does not appear to be fully controlled by total organic matter content, depositional environment or bioturbation. We argue that increased wildfire activity is likely caused by an increase in ignition of plant material as a result of an elevated number of lightning strikes. Global warming (caused by a massive input of carbon into the atmosphere, as indicated by carbon-isotope data) can increase storm activity, leading to increased numbers of lightning strikes. Previous Triassic-Jurassic Boundary wildfire studies have found fossil charcoal abundance peaks at other northern hemisphere sites (Denmark & Greenland), and concluded that they represent increases in wildfire activity in the earliest Jurassic. Our new charcoal and

  16. Sources, migration and transformation of antimony contamination in the water environment of Xikuangshan, China: Evidence from geochemical and stable isotope (S, Sr) signatures

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Bing [Geological Survey, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China); State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China); Zhou, Jianwei, E-mail: jw.zhou@cug.edu.cn [School of Environmental Studies, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China); Zhou, Aiguo; Liu, Cunfu [School of Environmental Studies, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China); Xie, Lina [School of Environmental Studies, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China); State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences (Wuhan), Lumo Rd 388, Wuhan 430074, Hubei (China)

    2016-11-01

    The Xikuangshan (XKS) mine in central China is the largest antimony (Sb) mine in the world. The mining activity has seriously contaminated the waters in the area. To determine the sources, migration and transformation of Sb contamination, 32 samples from groundwater (aquifer water), surface water and mine water were collected for water chemistry, trace element and S{sub SO4} and Sr stable isotope analyses. The results showed that the groundwater and surface water were in an oxidized environment. The S{sub SO4} and Sr isotope compositions in the water indicated that dissolved Sb and SO{sub 4}{sup 2} originated from sulfide mineral (Sb{sub 2}S{sub 3}) oxidation, whereas radiogenic Sr may have been sourced from silicified limestone and stibnite in the Shetianqiao aquifer. Furthermore, a positive correlation between δ{sup 34}S{sub SO4} and δ{sup 87}Sr values revealed that the Sr, S and Sb in the waters had a common contamination source, i.e., silicified limestone and stibnite, whereas the Sr, S and Sb in rock and ore were sourced from Proterozoic basement clastics. The analysis also indicated that the isotope composition of dissolved SO{sub 4}{sup 2} {sup −} had been influenced by slight bacterial SO{sub 4} reduction in the Magunao aquifer. Mining or rock collapse may have caused Shetianqiao aquifer water to contaminate the Magunao aquifer water via mixing. This study has demonstrated that the stable isotopes of {sup 34}S{sub SO4} and {sup 87}Sr, combined with hydrochemical methods, are effective in tracking the sources, migration and transformation of Sb contamination. - Highlights: • Mining activities at XKS mine have caused serious water contamination. • The characteristics of Sb contamination in water environment are still unclear. • Combine S isotopes of sulfate and Sr isotopes with hydrochemical methods. • Sr, S, and Sb in natural water had a common source: silicified limestone and stibnite. • Shetianqiao aquifer water contaminated the Magunao

  17. Lead and neodymium isotopic results from metabasalts of the Haveri Formation, southern Finland: evidence for Palaeoproterozoic enriched mantle

    Directory of Open Access Journals (Sweden)

    Vaasjoki, M.

    1999-06-01

    Full Text Available Tholeiitic metabasalts and coexisting sulphides have been analysed for their Pb and Nd isotopic compositions from the Proterozoic Haveri Formation, which forms the basal unit of the Tampere Schist Belt in southern Finland. Ten whole rock samples analysed for Pb isotopes form a sublinear array which yields rather uncertain age estimates in the 1900-2000 Ma range and lies on the 207Pb/204Pb vs. 206Pb/204Pb diagram well below the average global lead evolution curve. The initial lead isotopic composition inferred from the whole rock data and measured on chalcopyrite is the least radiogenic obtained from the Svecofennian domain, and precludes involvement of old upper crustal material in basalt genesis. This together with the geochemical composition and initial eNd (1900 of +0.5±0.6 suggest that the Haveri mafic metavolcanic rocks were not derived from convective MORB-type mantle. The source was rather a mantle, which had been enriched in LRE