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Sample records for isotope effect evidence

  1. Rotational dynamics in ammonia borane: Evidence of strong isotope effects

    Energy Technology Data Exchange (ETDEWEB)

    Cantelli, Rosario; Paolone, Annalisa; Palumbo, Oriele; Leardini, F.; Autrey, Thomas; Karkamkar, Abhijeet J.; Luedtke, Avery T.

    2013-12-15

    This work reports anelastic spectroscopy measurements on the partially deuterated (ND3BH3 and NH3BD3) and perdeuterated (ND3BD3) ammonia borane (NH3BH3) compounds. The relaxations previously reported in NH3BH3 are observed in all the samples, and are ascribed to the rotational and torsional dynamics of NH(D)3BH(D)3 complexes. A new thermally activated peak appears at 70 K (for a vibration frequency of 1 kHz) in the spectrum of NH3BD3 and ND3BD3. The peak is practically a single-time Debye process, indicating absence of interaction between the relaxing units, and has a strikingly high intensity. A secondary relaxation process is also detected around 55 K. The anelastic spectrum of the ND3BH3 only displays this less intense process at 55 K. The analysis of the peaks supplies information about the dynamics of the relaxing species, and the obtained results provide indications on the effect of partial and selective deuteration on the hydrogen (deuterium) dynamics.

  2. Is there a stable isotope evidence for the CO2 fertiliser effect

    Indian Academy of Sciences (India)

    R V Krishnamurthy; M Machavaram

    2000-03-01

    It has been suggested that part of the so-called ``missing sink" of carbon dioxide introduced into the atmosphere by anthropogenic activities, that is the imbalance between estimated anthropogenic carbon dioxide emissions and oceanic uptake, may be stored in the vegetation in midlatitudes. Precise mecha- nisms of abstraction of additional carbon dioxide by vegetation, also known as the ``fertilization effect", are poorly understood. 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 concentration of carbon dioxide increased due to an increase in stomatal opening. Although increased intercellular concentration of carbon dioxide translated to increased Water Use Efficiency and assimilation rates, it also resulted in increased transpiration rate as shown by higher D/H of the fixed carbon. The two-fold significance of the isotope data are: first, they provide the first field evidence based on isotope studies for excess CO2 induced biomass production and second, they suggest that this mechanism is likely to operate only in limited environments. Vegetation in regions where mois- ture availability is not restricted so that there can be a gain in water use efficiency despite increased leaf evaporation are best suited to sequester excess carbon from the atmosphere.

  3. Garnet effect on Nd-Hf isotope decoupling: Evidence from the Jinfosi batholith, Northern Tibetan Plateau

    Science.gov (United States)

    Huang, Hui; Niu, Yaoling; Mo, Xuanxue

    2017-03-01

    The initial Nd and Hf isotope ratios of a 420 Ma post-collisional dioritic-granitic batholith from the Northern Tibetan plateau define a negative trend above and orthogonal to the ԐHf(t)-ԐNd(t) terrestrial array. This uncommon trend offers an insight into the origin of the puzzling Nd-Hf isotope decoupling in the crustal rocks. On this trend, samples depleted in heavy rare earth elements (HREEs, i.e., [Dy/Yb]N ≫ 1) deviate most from the terrestrial array whereas samples with flat HREEs (i.e., [Dy/Yb]N ≥ 1) deviate less or plot within the terrestrial array, pointing to the controlling effect of garnet in the magma source. Ancient garnet-bearing residues after melt extraction will have elevated Lu/Hf ratios and can evolve with time to produce high ԐHf(t) at a low ԐNd(t) value. Mixing of melts derived from such source lithologies (high Lu/Hf) with melts possessing a within-terrestrial array Nd-Hf isotopic composition (low Lu/Hf) best explains the observed trend orthogonal to the terrestrial array. The samples from the Jinfosi batholith with the most decoupled Nd-Hf isotope compositions require a larger degree (> 40%) and ancient (i.e., ≥ 1.8 Gyr) previous melt extraction from their source. It follows that the ancient melts with depleted HREEs complementary to those garnet-bearing residues should have low ԐHf values and plot below the terrestrial array, which is indeed shown by some Archean/Paleoproterozic TTGs.

  4. 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.

  5. [Carbon isotope (13C/12C) effect of photorespiration in photosynthetic organisms. Evidence for existence, probable mechanism].

    Science.gov (United States)

    Ivlev, A A

    2002-01-01

    Experimental evidence in favor of the new phenomenon predicted for photosynthesizing organisms, the fractionation of carbon isotopes in photorespiration is presented. A possible mechanism of this process is discussed. The fractionation of carbon in isotopes photorespiration occurs in the oxygenase phase of the functioning of ribulosebisphosphate carboxylase/oxygenase (rubisco), the key enzyme of photosynthesis, which is capable to act as carboxylase and oxygenase. Which function of the enzyme is active depends on CO2/O2 concentration ratio, which periodically changes in a cell. The key reaction in the mechanism of carbon isotope fractionation in photorespiration is glycine decarboxylation, which results in the splitting and removal from the cell of CO2 enriched with 12C and the accumulation of 13C photorespiratory carbon flow. The coupling of photorespiration and CO2 photoassimilation gives rise to two isotopically different carbon flows, which fill up separate carbohydrate pools, which are the sources of carbon in the following syntheses in the dark phase of photosynthesis. This enables one to identify, from the carbon isotope ratio of metabolites, their involvement in the photorespiratory and assimilatory carbon flows, to investigate the pathways of carbon metabolism, and to estimate more thoroughly the biosynthetic role of photorespiration.

  6. Isotope Effects in ESR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Werner Herrmann

    2013-06-01

    Full Text Available In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii the main characteristics of the generalized isotope effects are worked out, and finally (iii the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.

  7. 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.

  8. Isotopic evidence of early hominin diets

    Science.gov (United States)

    Sponheimer, Matt; Alemseged, Zeresenay; Cerling, Thure E.; Grine, Frederick E.; Kimbel, William H.; Leakey, Meave G.; Lee-Thorp, Julia A.; Kyalo Manthi, Fredrick; Reed, Kaye E.; Wood, Bernard A.; Wynn, Jonathan G.

    2013-06-01

    Carbon isotope studies of early hominins from southern Africa showed that their diets differed markedly from the diets of extant apes. Only recently, however, has a major influx of isotopic data from eastern Africa allowed for broad taxonomic, temporal, and regional comparisons among hominins. Before 4 Ma, hominins had diets that were dominated by C3 resources and were, in that sense, similar to extant chimpanzees. By about 3.5 Ma, multiple hominin taxa began incorporating 13C-enriched [C4 or crassulacean acid metabolism (CAM)] foods in their diets and had highly variable carbon isotope compositions which are atypical for African mammals. By about 2.5 Ma, Paranthropus in eastern Africa diverged toward C4/CAM specialization and occupied an isotopic niche unknown in catarrhine primates, except in the fossil relations of grass-eating geladas (Theropithecus gelada). At the same time, other taxa (e.g., Australopithecus africanus) continued to have highly mixed and varied C3/C4 diets. Overall, there is a trend toward greater consumption of 13C-enriched foods in early hominins over time, although this trend varies by region. Hominin carbon isotope ratios also increase with postcanine tooth area and mandibular cross-sectional area, which could indicate that these foods played a role in the evolution of australopith masticatory robusticity. The 13C-enriched resources that hominins ate remain unknown and must await additional integration of existing paleodietary proxy data and new research on the distribution, abundance, nutrition, and mechanical properties of C4 (and CAM) plants.

  9. Palaeoclimatic and deforestation effect on the coastal fresh groundwater resources of SE Ivory Coast from isotopic and chemical evidence

    Science.gov (United States)

    Adiaffi, Bernard; Marlin, Christelle; Oga, Yéï Marie Solange; Massault, Marc; Noret, Aurelie; Biemi, Jean

    2009-05-01

    SummaryIn the South-east of the Ivory Coast, two aquifer systems have been studied in the sedimentary deposits at the South and in the fractured bedrock at the North of the study area (5-6°N, 2.40-4.40°W) : (1) the Continental Terminal (CT) and (2) the Paleoproterozoïc Bedrock (PB). In the studied area, the vegetation cover has undergone significant changes since 1955 in addition to climate change. Rainforests have gradually disappeared due to natural and anthropological deforestation. The impact of deforestation on groundwater of the PB and on the CT has been studied by a geochemical approach. Stable isotopes ( 18O, 2H and 13C) contents, radiocarbon ( 14C) contents and chemical data (major ions) have been measured on a set of 25 groundwater samples. The residence time of the groundwaters is estimated with the 14C using two models: (i) the model of well-mixed reservoir (WMR model) and (ii) the piston flow model (PF model). The range of the PB groundwater residence time (15,200-8300 to ˜300-100 a BP) for both models shows that the recharge has started at the beginning of the post-glacial period whereas the CT aquifer recharge is much more recent (from 300 a BP to today). The PB groundwater provides information about paleoclimatic conditions that occurred over the studied area during the late Pleistocene. The low contents indicate cold and/or more humid conditions of recharge. During that period, the low content of 13C is consistent with a vegetation cover dominated by rainforest (C 3 plants). After the 20th century, the progressive evolution of vegetation cover from forest to cultivated plants and grasses is shown by the enrichment of groundwater in 13C (C 3 plants to C 4 plants). The relatively high mineralization level (mean of 143.7 mg L -1) and high δ18O- δ2H values of modern PB groundwater reflect of a recharge process that is slowed by a thick layer (16.3-72.5 m) of weathered formations above the PB formations. Groundwaters of the CT aquifer are

  10. The process of glauconitization: chemical and isotopic evidence

    Science.gov (United States)

    Stille, Peter; Clauer, Norbert

    1994-08-01

    Sequential leaching experiments were made on Recent glauconies and clay fractions of the associated mud from off-shore Africa near the estuary of the Congo River. Analyses of major/rare earth elements (REE) and Nd isotopic compositions on the resulting leachate and residue pairs allow identification of at least three important and isotopically distinct components which contributed to the glauconitization process: (1) a detrital component with relatively high 87Sr/86Sr and relatively low 143Nd/144Nd isotopic ratios; (2) a phosphate phase rich in REE and Sr with sea water Sr and Nd isotopic characteristics; (3) a component rich in organic matter and Ca with a sea water Sr isotopic signature, a relatively low Nd isotopic composition and elevated Sm/Nd ratios. This latter component probably represents the suspended organic and carbonate-rich river load. The detrital and the river components were mixed up in the muddy off-shore sediment, ingested by worms, and integrated into faecal pellets. The resulting material has Sr and Nd isotopic signatures intermediate between those of the detrital and river components, and represents the precursor of the glaucony minerals. During the subsequent dissolution-crystallization process, the glauconitic pellets remain isotopically closed to any external supply, but expulsion of Sr and Nd with increasing degree of maturation is observed without any effect on the Sr and Nd isotopic compositions. At a higher maturation stage (K2O>4.5%), the Sr and Nd isotopic compositions tend to decrease and increase, respectively, approximating the isotopic composition values of the phosphate-rich phase. Because the Sr and Nd concentrations decrease, the evolution of the glauconies toward lower Sr and higher Nd isotopic compositions can only be explained by expulsion of Sr and Nd of the detrital component with high Sr and low Nd isotopic signatures. Dissolution of the chemically unstable, wormdigested clay material from mud may be responsible for the

  11. Combinatorial effects on clumped isotopes and their significance in biogeochemistry

    Science.gov (United States)

    Yeung, Laurence Y.

    2016-01-01

    The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial

  12. Heavy atom isotope effects on enzymatic reactions

    Science.gov (United States)

    Paneth, Piotr

    1994-05-01

    The theory of isotope effects, which has proved to be extremely useful in providing geometrical details of transition states in a variety of chemical reactions, has recently found an application in studies of enzyme-catalyzed reactions. These reactions are multistep in nature with few steps being partially rate-limiting, thus interpretation of these isotope effects is more complex. The theoretical framework of heavy-atom isotope effects on enzymatic reactions is critically analyzed on the basis of recent results of: carbon kinetic isotope effects on carbonic anhydrase and catalytic antibodies; multiple carbon, deuterium isotope effects on reactions catalyzed by formate decarboxylase; oxygen isotope effects on binding processes in reactions catalyzed by pyruvate kinase; and equilibrium oxygen isotope effect on binding an inhibitor to lactate dehydrogenase. The advantages and disadvantages of reaction complexity in learning details of formal and molecular mechanisms are discussed in the examples of reactions catalyzed by phosphoenolpyruvate carboxylase, orotidine decarboxylase and glutamine synthetase.

  13. Osmium isotope evidence for a large Late Triassic impact event

    Science.gov (United States)

    Sato, Honami; Onoue, Tetsuji; Nozaki, Tatsuo; Suzuki, Katsuhiko

    2013-01-01

    Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio (187Os/188Osi) of ∼0.477 to unradiogenic values of ∼0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous–Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3–7.8 km in diameter) produced a global decrease in seawater 187Os/188Os ratios in the Late Triassic. PMID:24036603

  14. Paleoclimate and Amerindians: evidence from stable isotopes and atmospheric circulation.

    Science.gov (United States)

    Lovvorn, M B; Frison, G C; Tieszen, L L

    2001-02-27

    Two Amerindian demographic shifts are attributed to climate change in the northwest plains of North America: at approximately 11,000 calendar years before present (yr BP), Amerindian culture apparently split into foothills-mountains vs. plains biomes; and from 8,000-5,000 yr BP, scarce archaeological sites on the open plains suggest emigration during xeric "Altithermal" conditions. We reconstructed paleoclimates from stable isotopes in prehistoric bison bone and relations between weather and fractions of C(4) plants in forage. Further, we developed a climate-change model that synthesized stable isotope, existing qualitative evidence (e.g., palynological, erosional), and global climate mechanisms affecting this midlatitude region. Our isotope data indicate significant warming from approximately 12,400 to 11,900 yr BP, supporting climate-driven cultural separation. However, isotope evidence of apparently wet, warm conditions at 7,300 yr BP refutes emigration to avoid xeric conditions. Scarcity of archaeological sites is best explained by rapid climate fluctuations after catastrophic draining of the Laurentide Lakes, which disrupted North Atlantic Deep Water production and subsequently altered monsoonal inputs to the open plains.

  15. Isotope and multiband effects in layered superconductors.

    Science.gov (United States)

    Bussmann-Holder, Annette; Keller, Hugo

    2012-06-13

    In this review we consider three classes of superconductors, namely cuprate superconductors, MgB(2) and the new Fe based superconductors. All of these three systems are layered materials and multiband compounds. Their pairing mechanisms are under discussion with the exception of MgB(2), which is widely accepted to be a 'conventional' electron-phonon interaction mediated superconductor, but extending the Bardeen-Cooper-Schrieffer (BCS) theory to account for multiband effects. Cuprates and Fe based superconductors have higher superconducting transition temperatures and more complex structures. Superconductivity is doping dependent in these material classes unlike in MgB(2) which, as a pure compound, has the highest values of T(c) and a rapid suppression of superconductivity with doping takes place. In all three material classes isotope effects have been observed, including exotic ones in the cuprates, and controversial ones in the Fe based materials. Before the area of high-temperature superconductivity, isotope effects on T(c) were the signature for phonon mediated superconductivity-even when deviations from the BCS value to smaller values were observed. Since the discovery of high T(c) materials this is no longer evident since competing mechanisms might exist and other mediating pairing interactions are discussed which are of purely electronic origin. In this work we will compare the three different material classes and especially discuss the experimentally observed isotope effects of all three systems and present a rather general analysis of them. Furthermore, we will concentrate on multiband signatures which are not generally accepted in cuprates even though they are manifest in various experiments, the evidence for those in MgB(2), and indications for them in the Fe based compounds. Mostly we will consider experimental data, but when possible also discuss theoretical models which are suited to explain the data.

  16. Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

    Science.gov (United States)

    Freeman, K. H.; Hayes, J. M.; Trendel, J. M.; Albrecht, P.

    1990-01-01

    The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

  17. Analysis of solvent nucleophile isotope effects: evidence for concerted mechanisms and nucleophilic activation by metal coordination in nonenzymatic and ribozyme-catalyzed phosphodiester hydrolysis.

    Science.gov (United States)

    Cassano, Adam G; Anderson, Vernon E; Harris, Michael E

    2004-08-17

    Heavy atom isotope effects are a valuable tool for probing chemical and enzymatic reaction mechanisms; yet, they are not widely applied to examine mechanisms of nucleophilic activation. We developed approaches for analyzing solvent (18)O nucleophile isotope effects ((18)k(nuc)) that allow, for the first time, their application to hydrolysis reactions of nucleotides and nucleic acids. Here, we report (18)k(nuc) for phosphodiester hydrolysis catalyzed by Mg(2+) and by the Mg(2+)-dependent RNase P ribozyme and deamination by the Zn(2+)-dependent protein enzyme adenosine deaminase (ADA). Because ADA incorporates a single solvent molecule into the product inosine, this reaction can be used to monitor solvent (18)O/(16)O ratios in complex reaction mixtures. This approach, combined with new methods for analysis of isotope ratios of nucleotide phosphates by whole molecule mass spectrometry, permitted determination of (18)k(nuc) for hydrolysis of thymidine 5'-p-nitrophenyl phosphate and RNA cleavage by the RNase P ribozyme. For ADA, an inverse (18)k(nuc) of 0.986 +/- 0.001 is observed, reflecting coordination of the nucleophile by an active site Zn(2+) ion and a stepwise mechanism. In contrast, the observed (18)k(nuc) for phosphodiester reactions were normal: 1.027 +/- 0.013 and 1.030 +/- 0.012 for the Mg(2+)- and ribozyme-catalyzed reactions, respectively. Such normal effects indicate that nucleophilic attack occurs in the rate-limiting step for these reactions, consistent with concerted mechanisms. However, these magnitudes are significantly less than the (18)k(nuc) observed for nucleophilic attack by hydroxide (1.068 +/- 0.007), indicating a "stiffer" bonding environment for the nucleophile in the transition state. Kinetic analysis of the Mg(2+)-catalyzed reaction indicates that a Mg(2+)-hydroxide complex is the catalytic species; thus, the lower (18)k(nuc), in large part, reflects direct metal ion coordination of the nucleophilic oxygen. A similar value for the RNase P

  18. Oxygen isotope evidence for shallow emplacement of Adirondack anorthosite

    Science.gov (United States)

    Valley, J.W.; O'Neil, J.R.

    1982-01-01

    Oxygen isotopic analysis of wollastonites from the Willsboro Mine, Adirondack Mountains, New York reveals a 400-ft wide zone of 18O depletion at anorthosite contacts. Values of ??18O vary more sharply with distance and are lower (to -1.3) than any yet reported for a granulite fades terrain. Exchange with circulating hot meteoric water best explains these results and implies that the anorthosite was emplaced at relatively shallow depths, granulite fades metamorphism (23 km). These 18O depletions offer the first strong evidence for shallow emplacement of anorthosite within the Grenville Province and suggest that regional metamorphism was a later and tectonically distinct event. ?? 1982 Nature Publishing Group.

  19. Isotope effects of hydrogen and atom tunnelling

    Science.gov (United States)

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

    2016-06-01

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

  20. Oxygen isotope effects in Ba1-xKxBiO3 high-temperature superconductors: Evidence for unconventional phonon-mediated pairing mechanism

    Science.gov (United States)

    Derimow, Nicholas; Aguilar, Victor; Khodagulyan, Armond; Labry, Jacob; Zhao, Guo-Meng

    2014-03-01

    The microscopic pairing mechanism for high-temperature superconductivity in magnetic copper and iron-based superconductors remains elusive despite tremendous experimental and theoretical efforts. The electron-phonon coupling constants predicted from the local density approximation (LDA) are too small to explain high-temperature superconductivity. On the other hand, high-temperature superconductivity in non-magnetic bismuth-based superconductors is believed to be phonon-mediated while the electron-phonon coupling constant predicted from the LDA is also too small (about 0.30) to explain superconductivity. We report magnetic and thermal properties of the oxygen-isotope exchanged Ba1-xKxBiO3 (x = 0.37 and 0.40) high-temperature superconductors to elucidate the pairing mechanism of this material. The deduced thermodynamic critical fields, electronic specific heat anomalies, superconducting transition temperatures, and magnetic penetration depths of the 16O and 18O samples are consistent with a phonon-mediated pairing mechanism with the effective electron-phonon coupling constant of about 1.0. We also show that the enhanced electron-phonon coupling constant may arise from the lattice polaronic effect, which increases the density of states at Fermi level. This research is funded by NIH grant (R25 GM 061331).

  1. Lead isotopic evidence for selective uptake of radium in illite

    Energy Technology Data Exchange (ETDEWEB)

    Hidaka, H.; Horie, K. [Department of Earth and Planetary Systems Science, Hiroshima University Higashi-Hiroshima 739-8526 (Japan); Gauthier-Lafaye, F. [Centre de Geochimie de la Surface, UMR7517-CNRS-ULP, 67084 Strasbourg (France)

    2005-07-01

    Full text of publication follows: Radium has no stable isotopes. {sup 226}Ra having the longest half-life (T{sub 1/2} = 1600 year) among radium radioisotopes exists as a precursor of decay product from {sup 238}U in nature, and finally decays to the stable isotope {sup 206}Pb. Long-lived nuclides such as {sup 226}Ra may be profoundly fractionated from their parents in association with intense geochemical events in the terrestrial environments. Enrichment of Ra resulted from vegetation cycle and selective uptake into clay minerals has been reported [1,2]. It is of particular interest to understand the geochemical behaviors of Ra from the viewpoint of long-termed repository safety of radio-nuclear waste. We report here geochemical evidence of selective uptake of Ra ({sup 226}Ra) into clay minerals studied from the Pb isotopic compositions. The sample from sandstone layer at underground drift close to natural reactor zone 13 at the Oklo uranium deposits, Gabon. Several tiny illite grains sized about 100 {mu}m were found in fine calcite veins with 0.1 to 2 mm width in quartz matrix texture. Isotopic analyses of Pb and some related elements (U, Rb, Sr, Cs and Ba) in individual minerals were carried out by a Sensitive High Resolution Ion Microprobe (SHRIMP) at Hiroshima University. The Pb isotopic data of quartz and calcite in the sample provide the geochronological information corresponding to the formation of 2.15 billion year-old basement rocks and the occurrence of later hydrothermal activity in this region at 0.88 billion years, respectively. On the other hand, illite shows high enrichment of {sup 206}Pb, which cannot be explained simply from normal U decays. {sup 206}Po-enriched illite grains also show a strong enrichment of Ba. Such an enrichment of Ba is not observed in the neighboring minerals of illite grains. Considering that Ba has been used as a chemical tracer of {sup 226}Ra because of the chemical similarities between Ba and Ra, our result strongly

  2. The isotope effect: Prediction, discussion, and discovery

    CERN Document Server

    Kragh, Helge

    2011-01-01

    The precise position of a spectral line emitted by an atomic system depends on the mass of the atomic nucleus and is therefore different for isotopes belonging to the same element. The possible presence of an isotope effect followed from Bohr's atomic theory of 1913, but it took several years before it was confirmed experimentally. Its early history involves the childhood not only of the quantum atom, but also of the concept of isotopy. Bohr's prediction of the isotope effect was apparently at odds with early attempts to distinguish between isotopes by means of their optical spectra. However, in 1920 the effect was discovered in HCl molecules, which gave rise to a fruitful development in molecular spectroscopy. The first detection of an atomic isotope effect was no less important, as it was by this means that the heavy hydrogen isotope deuterium was discovered in 1932. The early development of isotope spectroscopy illustrates the complex relationship between theory and experiment, and is also instructive with...

  3. Newtonian kinetic isotope effects. Observation, prediction, and origin of heavy-atom dynamic isotope effects.

    Science.gov (United States)

    Kelly, Kelmara K; Hirschi, Jennifer S; Singleton, Daniel A

    2009-06-24

    Intramolecular (13)C kinetic isotope effects were determined for the dimerization of cyclopentadiene. Substantial isotope effects were observed in three positions, despite the C(2) symmetry of the cycloaddition transition state and the absence of dynamical bottlenecks after this transition state. The observed isotope effects were predicted well from trajectory studies by extrapolating the outcomes of trajectories incorporating superheavy isotopes of carbon, ranging from (20)C to (140)C. Trajectory studies suggest that the isotope effects are unrelated to zero-point energy or the geometrical and momentum properties of the transition state. However, steepest-descent paths in mass-weighted coordinates correctly predict the direction of the isotope effects, supporting a novel origin in Newton's second law of motion.

  4. 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...... or moderate, and overall sulfur fractionation in the stratosphere is very weak which does not exclude OCS from being an acceptable background the Stratospheric Sulfate Aerosol layer. (iii) CO2 photolysis in the upper stratosphere and lower mesosphere is highly fractionating in both isotopes, enriching...

  5. Hydrogen isotope effect on the Dimits shift

    Science.gov (United States)

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

    2016-10-01

    The hydrogen isotope effect on the Dimits shift in drift wave turbulence (Dimits et al 2000 Phys. Plasmas 7 969) is discussed using the theory of zonal flows, in which the nonlinear damping rate of zonal flows is taken into account. The up-shift of the critical linear growth rate of the drift waves, above which drift wave fluctuations develop, is investigated. The dependence on the mass number of the hydrogen isotope is discussed.

  6. ZIRCONIUM—HAFNIUM ISOTOPE EVIDENCE FROM METEORITES FOR THE DECOUPLED SYNTHESIS OF LIGHT AND HEAVY NEUTRON-RICH NUCLEI

    Energy Technology Data Exchange (ETDEWEB)

    Akram, W.; Schönbächler, M. [School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Sprung, P. [Institut für Planetologie, Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Vogel, N. [Institute for Geochemistry and Petrology, ETH, Clausiusstrasse 25, 8092 Zürich (Switzerland)

    2013-11-10

    Recent work based on analyses of meteorite and terrestrial whole-rock samples showed that the r- and s- process isotopes of Hf were homogeneously distributed throughout the inner solar system. We report new Hf isotope data for Calcium-Aluminum-rich inclusions (CAIs) of the CV3 carbonaceous chondrite Allende, and novel high-precision Zr isotope data for these CAIs and three carbonaceous chondrites (CM, CO, CK). Our Zr data reveal enrichments in the neutron-rich isotope {sup 96}Zr (≤1ε in {sup 96}Zr/{sup 90}Zr) for bulk chondrites and CAIs (∼2ε). Potential isotope effects due to incomplete sample dissolution, galactic and cosmic ray spallation, and the nuclear field shift are assessed and excluded, leading to the conclusion that the {sup 96}Zr isotope variations are of nucleosynthetic origin. The {sup 96}Zr enrichments are coupled with {sup 50}Ti excesses suggesting that both nuclides were produced in the same astrophysical environment. The same CAIs also exhibit deficits in r-process Hf isotopes, which provides strong evidence for a decoupling between the nucleosynthetic processes that produce the light (A ≤ 130) and heavy (A > 130) neutron-rich isotopes. We propose that the light neutron-capture isotopes largely formed in Type II supernovae (SNeII) with higher mass progenitors than the supernovae that produced the heavy r-process isotopes. In the context of our model, the light isotopes (e.g. {sup 96}Zr) are predominantly synthesized via charged-particle reactions in a high entropy wind environment, in which Hf isotopes are not produced. Collectively, our data indicates that CAIs sampled an excess of materials produced in a normal mass (12-25 M{sub ☉}) SNII.

  7. Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

    Science.gov (United States)

    Valley, J.W.; O'Neil, J.R.

    1984-01-01

    The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks. Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed. Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ??18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences. The range of Adirondack carbonate ??18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their

  8. 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.

  9. Isotope effects of hafnium in solvent extraction using crown ethers

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Toshiyuki; Moriyama, Hirotake [Research Reactor Institute, Kyoto University, Osaka (Japan); Hirata, Takafumi [Laboratory for Planetary Sciences, Tokyo Institute of Technology, Tokyo (Japan); Nishizawa, Kazushige [Department of Nuclear Engineering, Graduate School of Engineering, Osaka University, Osaka (Japan)

    2001-06-01

    Hafnium isotopes were fractionated in a liquid-liquid extraction system by using seven types of crown ethers, tributyl phosphate, or {omicron}-diethoxybenzene. The largest isotope effect was observed in the isotope pair of {sup 177}Hf-{sup 179}Hf with dibenzo-24-crown-8; the isotope enrichment factor was observed to be 0.0129{+-}0.0032. (author)

  10. Isotope effects in a multicusp tandem ion source

    Energy Technology Data Exchange (ETDEWEB)

    Graham, W.G. (Department of Pure and Applied Physics, Queen' s University, Belfast BT7 1NN (Northern Ireland))

    1992-10-05

    Measurements of plasma parameters, including electron density, electron energy distribution function (eedf), and negative ion density, have been made in the driver and extractor regions of a multicusp tandem ion source. Here results which focus on comparing operation in hydrogen and deuterium are presented. Several isotope effects are evident. In particular, for the same operating conditions, the electron density is found to be higher in deuterium than in hydrogen while the negative ion density is consistently lower.

  11. 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

    by contemporaneous mafic magmas; the transition between the two now preserved as a zone of chilled mafic sheets and pillows in granite. Mafic components have highly variably isotopic compositions as a result of contamination either at depth or following injection into the magma chamber. Intermediate dikes...... 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...... lithologies have Nd isotopic compositions (eNd=+3.5) that are the lowest in the region and similar to the granite and suggestive of prolonged interactions and homogenization of the two components. Sr and Nd isotopic data for felsic enclaves are inconsistent with previously suggested models of diffusional...

  12. Silicon isotope evidence against an enstatite chondrite Earth.

    Science.gov (United States)

    Fitoussi, Caroline; Bourdon, Bernard

    2012-03-23

    The compositions of Earth materials are strikingly similar to those of enstatite chondrite meteorites in many isotope systems. Although this suggests that Earth largely accreted from enstatite chondrites, definitive proof of this model has been lacking. By comparing the silicon (Si) isotope signatures of several extraterrestrial materials with terrestrial samples, we show that they cannot be explained by core-formation scenarios involving a bulk Earth of enstatite chondrite composition. Si isotope similarities between the bulk silicate Earth and the Moon preclude the existence of a hidden reservoir in the lower mantle, a necessary condition of the enstatite chondrite model, and require an equilibrium process after the Moon-forming impact. A three-end-member chondritic mixing model for Earth reconciles the Si isotope similarities between enstatite chondrites and Earth.

  13. 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...

  14. Isotopic evidence of Cr partitioning into Earth's core.

    Science.gov (United States)

    Moynier, Frederic; Yin, Qing-Zhu; Schauble, Edwin

    2011-03-18

    The distribution of chemical elements in primitive meteorites (chondrites), as building blocks of terrestrial planets, provides insight into the formation and early differentiation of Earth. The processes that resulted in the depletion of some elements [such as chromium (Cr)] in the bulk silicate Earth relative to chondrites, however, remain debated between leading candidate causes: volatility versus core partitioning. We show through high-precision measurements of Cr stable isotopes in a range of meteorites, which deviate by up to ~0.4 per mil from those of the bulk silicate Earth, that Cr depletion resulted from its partitioning into Earth's core, with a preferential enrichment in light isotopes. Ab initio calculations suggest that the isotopic signature was established at mid-mantle magma ocean depth as Earth accreted planetary embryos and progressively became more oxidized.

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

    Science.gov (United States)

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

    2010-10-01

    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.

  16. Arctic methane sources: Isotopic evidence for atmospheric inputs

    NARCIS (Netherlands)

    Fisher, R.E.; Sriskantharajah, S.; Lowry, D.; Lanoisellé, M.; Fowler, C.M.R.; James, R.H.; Hermansen, O.; Lund Myhre, C.; Stohl, A.; Greinert, J.; Nisbet-Jones, P.B.R.; Mienert, J.; Nisbet, E.G.

    2011-01-01

    By comparison of the methane mixing ratio and the carbon isotope ratio (delta C-13(CH4)) in Arctic air with regional background, the incremental input of CH4 in an air parcel and the source delta C-13(CH4) signature can be determined. Using this technique the bulk Arctic CH4 source signature of air

  17. Runoff generation mechanism at two distinct headwater catchments - isotopic evidence

    Science.gov (United States)

    Dohnal, Michal; Votrubová, Jana; Šanda, Martin; Tesař, Miroslav; Vogel, Tomáš; Dušek, Jaromír

    2016-04-01

    Data from two headwater catchments indicate considerably different runoff formation mechanisms. The contributions of different surface and subsurface runoff mechanisms to the catchment discharge formation at these two small forested headwater catchments are studied with help of the natural isotopic signatures of the observed fluxes. The Uhlirska catchment (1.78 sq. km, Jizera Mts., Czech Republic) is situated in headwater area of Cerna Nisa stream. Deluviofluvial granitic sediments in the valley bottom areas (riparian zones/wetlands) are surrounded by gentle hillslopes with shallow soils developed on crystalline bedrock. The Liz catchment (0.99 sq. km, Bohemian Forest, Czech Republic) belongs to hillslope-type catchments without riparian zones situated in headwater area of Volynka River. The soil at Liz is developed on biotite paragneiss bedrock. Autocorrelation analysis of the measured catchment discharge rates reveals different hydrograph characteristics for each of the two catchments. Estimated autocorrelation lengths differ by an order of magnitude. Variations of oxygen-18 isotope concentrations in precipitation, groundwater and streamflow were analyzed. Several significant rainfall-runoff events at each of the two catchments were analyzed in detail. These events exhibit substantial difference in isotopic compositions of event and pre-event water, which facilitates hydrograph separation. Clockwise and counterclockwise hysteretic relationships between the stream discharge and its isotope concentration were identified. Results were confronted with the previously published concepts of the runoff formation at the catchments under study. The research was funded by the Czech Science Foundation, project No. 14-15201J.

  18. 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 unradiogeni...

  19. Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

    Science.gov (United States)

    Des Marais, D. J.; Donchin, J. H.; Nehring, N. L.; Truesdell, A. H.

    1981-01-01

    Isotopic measurements of individual geothermal hydrocarbons that are, as a group, of higher molecular weight than methane are reported. It is believed in light of this data that the principal source of hydrocarbons in four geothermal areas in western North America is the thermal decomposition of sedimentary or groundwater organic matter.

  20. Isotope evidence for N2-fixation in Sphagnum peat bogs

    Science.gov (United States)

    Novak, Martin; Jackova, Ivana; Buzek, Frantisek; Stepanova, Marketa; Veselovsky, Frantisek; Curik, Jan; Prechova, Eva

    2016-04-01

    Waterlogged organic soils store as much as 30 % of the world's soil carbon (C), and 15 % of the world's soil nitrogen (N). In the era of climate change, wetlands are vulnerable to increasing temperatures and prolonged periods of low rainfall. Higher rates of microbial processes and/or changing availability of oxygen may lead to peat thinning and elevated emissions of greenhouse gases (mostly CO2, but also CH4 and N2O). Biogeochemical cycling of C and N in peat bogs is coupled. Under low levels of pollution by reactive nitrogen (NO3-, NH4+), increasing N inputs may positively affect C storage in peat. Recent studies in North America and Scandinavia have suggested that pristine bogs are characterized by significant rates of microbial N2 fixation that augments C storage in the peat substrate. We present a nitrogen isotope study aimed at corroborating these findings. We conducted an isotope inventory of N fluxes and pools at two Sphagnum-dominated ombrotrophic peat bogs in the Czech Republic (Central Europe). For the first time, we present a time-series of del15N values of atmospheric input at the same locations as del15N values of living Sphagnum and peat. The mean del15N values systematically increased in the order: input NH4+ (-10.0 ‰) < input NO3- (-7.9 ‰) < peat porewater (-5.6 ‰) < Sphagnum (-5.0 ‰) < shallow peat (-4.2 ‰) < deep peat (-2.2 ‰) < runoff (-1.4 ‰) < porewater N2O (1.4 ‰). Importantly, N of Sphagnum was isotopically heavier than N of the atmospheric input (p < 0.001). If partial incorporation of reactive N from the atmosphere into Sphagnum was isotopically selective, the residual N would have to be isotopically extremely light. Such N, however, was not identified anywhere in the ecosystem. Alternatively, Sphagnum may have contained an admixture of isotopically heavier N from atmospheric N2 (del15N N2 = 0 ‰). We conlude that the N isotope systematics at the two Czech sites is consistent with the concept of significant N2 fixation

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

    Energy Technology Data Exchange (ETDEWEB)

    Matsuyama, M.; Kondo, M.; Noda, N. [Hydrogen Isotope Research Center, University of Toyama, Gofuku, Toyama (Japan); Tanaka, M.; Nishimura, K. [National Institute for Fusion Science, Toki-shi, Gifu (Japan)

    2015-03-15

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

  2. Lead isotopic evidence for evolutionary changes in magma-crust interaction, Central Andes, southern Peru

    Science.gov (United States)

    Barreiro, Barbara A.; Clark, Alan H.

    1984-07-01

    Lead isotopic measurements were made on Andean igneous rocks of Jurassic to Recent age in Moquegua and Tacna Departments, southernmost Peru, to clarify the petrogenesis of the rocks and, in particular, to investigate the effect of crustal thickness on rock composition. This location in the Cordillera Occidental is ideal for such a study because the ca. 2 Ga Precambrian basement rocks (Arequipa massif) have a distinct Pb isotopic signature which is an excellent tracer of crustal interaction, and because geomorphological research has shown that the continental crust was here thickened drastically in the later Tertiary. Seven samples of quartz diorites and granodiorites from the Ilo and Toquepala intrusive complexes, and seven samples of Toquepala Group subaerial volcanics were analyzed for Pb isotopic compositions. The plutonic rocks range in age from Jurassic to Eocene; the volcanic rocks are all Late Cretaceous to Eocene. With one exception, the Pb isotopic ratios are in the ranges 206Pb/ 204Pb= 18.52-18.75, 207Pb/ 204Pb= 15.58-15.65, and 208Pb/ 204Pb= 38.53-38.74. The data reflect very little or no interaction with old continental material of the Arequipa massif type. Lead from four Miocene Huaylillas Formation ash-flow tuffs, two Pliocene Capillune Formation andesites and five Quaternary Barroso Group andesites has lower 206Pb/ 204Pb than that in the pre-Miocene rocks, but relatively high 207Pb/ 204Pb and 208Pb/ 204Pb ( 206Pb/ 204Pb= 18.16-18.30, 207Pb/ 204Pb= 15.55-15.63, 208Pb/ 204Pb= 38.45-38.90). Tilton and Barreiro [9] have shown that contamination by Arequipa massif granulites can explain the isotopic composition of the Barosso Group lavas, and the new data demonstrate that this effect is evident, to varying degrees, in all the analysed Neogene volcanic rocks. The initial incorporation of such basement material into the magma coincided with the Early Miocene uplift of this segment of the Cordillera Occidental [32], and thus with the creation of a thick

  3. Persistently strong Indonesian Throughflow during marine isotope stage 3: evidence from radiogenic isotopes

    Science.gov (United States)

    Stumpf, Roland; Kraft, Steffanie; Frank, Martin; Haley, Brian; Holbourn, Ann; Kuhnt, Wolfgang

    2015-03-01

    The Indonesian Throughflow (ITF) connects the western Pacific Ocean with the eastern Indian Ocean, thus forming one of the major near surface current systems of the global thermohaline circulation. The intensity of the ITF has been found to be sensitive to changes in global ocean circulation, fluctuations in sea level, as well as to the prevailing monsoonal conditions of the Indonesian Archipelago and NW Australia. This study presents the first reconstruction of ITF dynamics combining radiogenic isotope compositions of neodymium (Nd), strontium (Sr), and lead (Pb) of the clay-size detrital fraction to investigate changes in sediment provenance, and paleo seawater Nd signatures extracted from the planktonic foraminifera and authigenic Fe-Mn oxyhydroxide coatings of the marine sediments focussing on marine isotope stage 3 (MIS3). Sediment core MD01-2378 was recovered within the framework of the International Marine Global Change Study (IMAGES) and is located in the area of the ITF outflow in the western Timor Sea (Scott Plateau, 13° 04.95‧ S and 121° 47.27‧ E, 1783 m water depth). In order to produce reliable seawater signatures, several extraction methods were tested against each other. The results of the study show that at this core location the extraction of surface water Nd isotope compositions from planktonic foraminifera is complicated by incomplete removal of contributions from Fe-Mn oxyhydroxides carrying ambient bottom water signatures. The bottom water Nd isotope signatures reliably obtained from the sediment coatings (average ɛNd = -5.0) document an essentially invariable water mass composition similar to today throughout the entire MIS3. The radiogenic Nd, Sr, and Pb isotope records of the clay-sized detrital fraction suggest that the Indonesian Archipelago rather than NW Australia was the main particle source at the location of core MD01-2378, and thus indicating a persistently strong ITF during MIS3. Furthermore, the variations of the detrital

  4. Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

    Science.gov (United States)

    Klemm, Veronika; Frank, Martin; Levasseur, Sylvain; Halliday, Alex N.; Hein, James R.

    2008-08-01

    Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10 Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10 Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12 Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the Nördlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum.

  5. Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

    Science.gov (United States)

    Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

    2014-01-01

    Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

  6. Isotope Effects of Solid Hydrogenic Pellet Ablation in Fusion Plasma

    Institute of Scientific and Technical Information of China (English)

    PENGLilin; DENGBaiquan; YANJiancheng; WANGXiaoyu

    2003-01-01

    The isotope effects of ablation processes in fusion plasma for five combinations of solid isotopic hydrogenic pellets H2, HD, D2,DT, T2 have been first time studied. The resuits show that the modifications caused by isotope effects for pellet erosion speeds range from 1 for hydrogen pellet down to 0. 487 for tritium pellet and are not negligible in ablation rate calculations. These effects lead to deeper mass deposition and improved core fueling efficiency.

  7. Stable isotope evidence for crustal recycling as recorded by superdeep diamonds

    Science.gov (United States)

    Burnham, A. D.; Thomson, A. R.; Bulanova, G. P.; Kohn, S. C.; Smith, C. B.; Walter, M. J.

    2015-12-01

    Sub-lithospheric diamonds from the Juina-5 and Collier-4 kimberlites and the Machado River alluvial deposit in Brazil have carbon isotopic compositions that co-vary with the oxygen isotopic compositions of their inclusions, which implies that they formed by a mixing process. The proposed model for this mixing process, based on interaction of slab-derived carbonate melt with reduced (carbide- or metal-bearing) ambient mantle, explains these isotopic observations. It is also consistent with the observed trace element chemistries of diamond inclusions from these localities and with the experimental phase relations of carbonated subducted crust. The 18O-enriched nature of the inclusions demonstrates that they incorporate material from crustal protoliths that previously interacted with seawater, thus confirming the subduction-related origin of superdeep diamonds. These samples also provide direct evidence of an isotopically anomalous reservoir in the deep (≥350 km) mantle.

  8. 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.

  9. 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.

  10. Quantum and isotope effects in lithium metal

    Science.gov (United States)

    Ackland, Graeme J.; Dunuwille, Mihindra; Martinez-Canales, Miguel; Loa, Ingo; Zhang, Rong; Sinogeikin, Stanislav; Cai, Weizhao; Deemyad, Shanti

    2017-06-01

    The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect-dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.

  11. Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean - Evidence from Pb-210 and stable Pb isotopes

    Science.gov (United States)

    Sherrell, Robert M.; Boyle, Edward A.; Hamelin, Bruno

    1992-01-01

    Vertical profiles of, on one hand, the stable Pb isotopic composition, and on the other, the ratio of total Pb to Pb-210 in suspended particles, are noted to closely track contemporaneous depth variations in these ratios for dissolved Pb throughout the upper 2 km of the Sargasso Sea near Bermuda. A simple flux model suggests that the effect of deep ocean scavenging processes on the flux and isotopic composition of Pb sinking on large particles was minor throughout the preanthropogenic, and most of the anthropogenic era: but it has become more important as surface inputs decrease to preleaded gasoline levels, perhaps exceeding the contribution of surface-derived Pb flux in the next decade.

  12. 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

  13. Spatial subsidies in spider diets vary with shoreline structure: Complementary evidence from molecular diet analysis and stable isotopes.

    Science.gov (United States)

    Hambäck, Peter A; Weingartner, Elisabeth; Dalén, Love; Wirta, Helena; Roslin, Tomas

    2016-12-01

    Inflow of matter and organisms may strongly affect the local density and diversity of organisms. This effect is particularly evident on shores where organisms with aquatic larval stages enter the terrestrial food web. The identities of such trophic links are not easily estimated as spiders, a dominant group of shoreline predator, have external digestion. We compared trophic links and the prey diversity of spiders on different shore types along the Baltic Sea: on open shores and on shores with a reed belt bordering the water. A priori, we hypothesized that the physical structure of the shoreline reduces the flow between ecosystem and the subsidies across the sea-land interface. To circumvent the lack of morphologically detectable remains of spider prey, we used a combination of stable isotope and molecular gut content analyses. The two tools used for diet analysis revealed complementary information on spider diets. The stable isotope analysis indicated that spiders on open shores had a marine signal of carbon isotopes, while spiders on reedy shores had a terrestrial signal. The molecular analysis revealed a diverse array of dipteran and lepidopteran prey, where spiders on open and reedy shores shared a similar diet with a comparable proportion of chironomids, the larvae of which live in the marine system. Comparing the methods suggests that differences in isotope composition of the two spider groups occurred because of differences in the chironomid diets: as larvae, chironomids of reedy shores likely fed on terrestrial detritus and acquired a terrestrial isotope signature, while chironomids of open shores utilized an algal diet and acquired a marine isotope signature. Our results illustrate how different methods of diet reconstruction may shed light on complementary aspects of nutrient transfer. Overall, they reveal that reed belts can reduce connectivity between habitats, but also function as a source of food for predators.

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

    Indian Academy of Sciences (India)

    K V Subbarao

    2000-03-01

    Similar Sr isotopic ratios (∼0.7055) for the tholeiite-spilite flow unit and the associated mineral phases, of Bombay (Deccan Traps) provide a direct evidence for the spilitic degradation of tholeiite. 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 process of spilitization is due to the reaction with a complex fluid having identical Sr-isotopic composition as that of the basaltic magma - thereby masking the details of the mixing process.

  15. 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.

  16. Evidence for Mo isotope fractionation in the solar nebula and during planetary differentiation

    Science.gov (United States)

    Burkhardt, Christoph; Hin, Remco C.; Kleine, Thorsten; Bourdon, Bernard

    2014-04-01

    Mass-dependent Mo isotope fractionation has been investigated for a wide range of meteorites including chondrites (enstatite, ordinary and carbonaceous chondrites), iron meteorites, and achondrites (eucrites, angrites and martian meteorites), as well as for lunar and terrestrial samples. Magmatic iron meteorites together with enstatite, ordinary and most carbonaceous chondrites define a common δMo value of -0.16±0.02‰ (relative to the NIST SRM 3134 Mo standard), which is interpreted to reflect the Mo isotope composition of bulk planetary bodies in the inner solar system. Heavy Mo isotope compositions for IAB iron meteorites most likely reflect impact-induced evaporative losses of Mo from these meteorites. Carbonaceous chondrites define an inverse correlation between δMo and metal content, and a positive correlation between δMo and matrix abundance. These correlations are mainly defined by CM and CK chondrites, and may reflect the heterogeneous distribution of an isotopically light metal and/or an isotopically heavy matrix component in the formation region of carbonaceous chondrites. Alternatively, the elevated δMo of the CM and CK chondrites could result from the loss of volatile, isotopically light Mo oxides, that formed under oxidized conditions typical for the formation of these chondrites. The Mo isotope compositions of samples derived from the silicate portion of differentiated planetary bodies are heavy compared to the mean composition of chondrites and iron meteorites. This difference is qualitatively consistent with experimental evidence for Mo isotope fractionation between metal and silicate. The common δMo values of -0.05±0.03‰ of lunar samples derived from different geochemical reservoirs indicate the absence of significant Mo isotope fractionation by silicate differentiation or impact metamorphism/volatilization on the Moon. The most straightforward interpretation of the Mo isotope composition of the lunar mantle corresponds to the formation

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

    Science.gov (United States)

    Deng, Kai; Yang, Shouye; Lian, Ergang; Li, Chao; Yang, Chengfan; Wei, Hailun

    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.

  18. Mantle fluids in the Karakoram fault: Helium isotope evidence

    Science.gov (United States)

    Klemperer, Simon L.; Kennedy, B. Mack; Sastry, Siva R.; Makovsky, Yizhaq; Harinarayana, T.; Leech, Mary L.

    2013-03-01

    The Karakoram fault (KKF) is the 1000 km-long strike-slip fault separating the western Himalaya from the Tibetan Plateau. From geologic and geodetic data, the KKF is argued either to be a lithospheric-scale fault with hundreds of km of offset at several cm/a, or to be almost inactive with cumulative offset of only a few tens of kilometers and to be just the upper-crustal localization of distributed deformation at depth. Here we show 3He/4He ratios in geothermal springs along a 500-km segment of the KKF are 3-100 times the normal ratio in continental crust, providing unequivocal evidence that a component of these hydrologic systems is derived from tectonically active mantle. Mantle enrichment is absent along the Indus-Yarlung suture zone (ISZ) just 35 km southwest of the KKF, suggesting that the mantle fluids flow only within the KKF. Within the last few Ma, the KKF must have accessed tectonically active Tibetan mantle northeast of the "mantle suture" which we therefore locate vertically beneath the KKF, very close to the surface trace of the ISZ. Hence, in southwestern Tibet, Indian crust may not now be underthrusting substantially north of the ISZ, even though Miocene underthrusting may have placed Indian crust north of the ISZ in the lower half of the Tibetan Plateau crust. This is in significant contrast to central and eastern Tibet where underthrust Indian material not only forms the lower half of the Tibetan crust but is also currently underthrusting for ∼200 km north of the ISZ. Our new constraint on KKF penetration to the mantle allows an improved description of the continuously evolving Karakoram fault, as a tectonically significant yet perhaps geologically ephemeral lithospheric structure.

  19. 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.

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

    Science.gov (United States)

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

    2011-05-01

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

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

    Indian Academy of Sciences (India)

    B Saritha; M Durga Prasad

    2012-01-01

    Recently, we had suggested that the motion along the promoter mode in the first part of the IRC of proton transfer reaction enhances the delocalization of electrons on the acceptor atom into the * orbital of the donor-hydrogen covalent bond, and as a consequence weakens it. This leads to a reduction of the barrier to the proton transfer as well as the stretching frequency of donor-hydrogen bond. 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 on three systems, (HF)3, formic acid dimer, and (H2O) clusters is provided to support this assertion.

  2. 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

  3. 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.

  4. Unified picture of the oxygen isotope effect in cuprate superconductors.

    Science.gov (United States)

    Chen, Xiao-Jia; Struzhkin, Viktor V; Wu, Zhigang; Lin, Hai-Qing; Hemley, Russell J; Mao, Ho-kwang

    2007-03-06

    High-temperature superconductivity in cuprates was discovered almost exactly 20 years ago, but a satisfactory theoretical explanation for this phenomenon is still lacking. The isotope effect has played an important role in establishing electron-phonon interaction as the dominant interaction in conventional superconductors. Here we present a unified picture of the oxygen isotope effect in cuprate superconductors based on a phonon-mediated d-wave pairing model within the Bardeen-Cooper-Schrieffer theory. We show that this model accounts for the magnitude of the isotope exponent as functions of the doping level as well as the variation between different cuprate superconductors. The isotope effect on the superconducting transition is also found to resemble the effect of pressure on the transition. These results indicate that the role of phonons should not be overlooked for explaining the superconductivity in cuprates.

  5. Methane Production Pathways in a California Rice Paddy: Isotopic Evidence for Substantial CO2 Reduction as Cause for Isotopically Light Emitted CH4 Carbon

    Science.gov (United States)

    Tyler, S. C.; McMillan, A. M.; Bearden, K.; Chidthaisong, A.; Macalady, J.

    2003-12-01

    We report measurements of δ 13C of emitted CH4 and sediment CH4 and CO2 during the 1999 rice-growing season near Maxwell, CA. Two treatments, one with rice straw incorporated from the previous season and one without rice straw were studied. The δ 13C value of emitted CH4 was consistently lighter isotopically (-67‰ to -83‰ throughout the season) in both straw incorporated and straw removed (burned) plots than in fields we have studied in Texas, Kenya, and Japan. Measured isotopic values of the production zone CH4 were compared to a two-point mixing curve representative of isotopic CH4 produced from either pure methyl-group fermentation or CO2 reduction pathways to partition the production pathways and to track seasonal changes in the production processes. Our sediment CH4 and CO2 isotope data indicate that fermentation was rarely the dominant methanogenic pathway - on the contrary CO2 reduction with H2 was more prevalent than fermentation methanogenesis throughout most of the season. The relatively isotopically light CH4 emitted by the paddy fields is also a product of oxidation and stem-transport processes which have isotopic effects of their own. These effects are discussed in context with the methanogenic isotope effects to provide a complete picture of the paddy field CH4 carbon isotope system.

  6. 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

  7. Isotopic Evidence for Early Trade in Animals between Old Kingdom Egypt and Canaan.

    Directory of Open Access Journals (Sweden)

    Elizabeth R Arnold

    Full Text Available Isotope data from a sacrificial ass and several ovicaprines (sheep/goat from Early Bronze Age household deposits at Tell es-Safi/Gath, Israel provide direct evidence for the movement of domestic draught/draft and husbandry animals between Old Kingdom Egypt (during the time of the Pyramids and Early Bronze Age III Canaan (ca. 2900-2500 BCE. Vacillating, bi-directional connections between Egypt and Canaan are known throughout the Early Bronze Age, but here we provide the first concrete evidence of early trade in animals from Egypt to Canaan.

  8. Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits.

    Science.gov (United States)

    Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

    2016-04-28

    Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ(114/110)Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ(114/110)Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits.

  9. Keratin decomposition by trogid beetles: evidence from a feeding experiment and stable isotope analysis

    Science.gov (United States)

    Sugiura, Shinji; Ikeda, Hiroshi

    2014-03-01

    The decomposition of vertebrate carcasses is an important ecosystem function. Soft tissues of dead vertebrates are rapidly decomposed by diverse animals. However, decomposition of hard tissues such as hairs and feathers is much slower because only a few animals can digest keratin, a protein that is concentrated in hairs and feathers. Although beetles of the family Trogidae are considered keratin feeders, their ecological function has rarely been explored. Here, we investigated the keratin-decomposition function of trogid beetles in heron-breeding colonies where keratin was frequently supplied as feathers. Three trogid species were collected from the colonies and observed feeding on heron feathers under laboratory conditions. We also measured the nitrogen (δ15N) and carbon (δ13C) stable isotope ratios of two trogid species that were maintained on a constant diet (feathers from one heron individual) during 70 days under laboratory conditions. We compared the isotopic signatures of the trogids with the feathers to investigate isotopic shifts from the feathers to the consumers for δ15N and δ13C. We used mixing models (MixSIR and SIAR) to estimate the main diets of individual field-collected trogid beetles. The analysis indicated that heron feathers were more important as food for trogid beetles than were soft tissues under field conditions. Together, the feeding experiment and stable isotope analysis provided strong evidence of keratin decomposition by trogid beetles.

  10. Oxygen and hydrogen isotope evidence for a temperate climate 3.42 billion years ago.

    Science.gov (United States)

    Hren, M T; Tice, M M; Chamberlain, C P

    2009-11-12

    Stable oxygen isotope ratios (delta(18)O) of Precambrian cherts have been used to establish much of our understanding of the early climate history of Earth and suggest that ocean temperatures during the Archaean era ( approximately 3.5 billion years ago) were between 55 degrees C and 85 degrees C (ref. 2). But, because of uncertainty in the delta(18)O of the primitive ocean, there is considerable debate regarding this conclusion. Examination of modern and ancient cherts indicates that another approach, using a combined analysis of delta(18)O and hydrogen isotopes (deltaD) rather than delta(18)O alone, can provide a firmer constraint on formational temperatures without independent knowledge of the isotopic composition of ambient waters. Here we show that delta(18)O and deltaD sampled from 3.42-billion-year-old Buck Reef Chert rocks in South Africa are consistent with formation from waters at varied low temperatures. The most (18)O-enriched Buck Reef Chert rocks record the lowest diagenetic temperatures and were formed in equilibrium with waters below approximately 40 degrees C. Geochemical and sedimentary evidence suggests that the Buck Reef Chert was formed in shallow to deep marine conditions, so our results indicate that the Palaeoarchaean ocean was isotopically depleted relative to the modern ocean and far cooler (

  11. Dietary resilience among hunter-gatherers of Tierra del Fuego: Isotopic evidence in a diachronic perspective.

    Science.gov (United States)

    Tafuri, Mary Anne; Zangrando, Atilio Francisco Javier; Tessone, Augusto; Kochi, Sayuri; Moggi Cecchi, Jacopo; Di Vincenzo, Fabio; Profico, Antonio; Manzi, Giorgio

    2017-01-01

    The native groups of Patagonia have relied on a hunter-gatherer economy well after the first Europeans and North Americans reached this part of the world. The large exploitation of marine mammals (i.e., seals) by such allochthonous groups has had a strong impact on the local ecology in a way that might have forced the natives to adjust their subsistence strategies. Similarly, the introduction of new foods might have changed local diet. These are the premises of our isotopic-based analysis. There is a large set of paleonutritional investigations through isotopic analysis on Fuegians groups, however a systematic exploration of food practices across time in relation to possible pre- and post-contact changes is still lacking. In this paper we investigate dietary variation in hunter-gatherer groups of Tierra del Fuego in a diachronic perspective, through measuring the isotopic ratio of carbon (∂13C) and nitrogen (∂15N) in the bone collagen of human and a selection of terrestrial and marine animal samples. The data obtained reveal an unexpected isotopic uniformity across prehistoric and recent groups, with little variation in both carbon and nitrogen mean values, which we interpret as the possible evidence of resilience among these groups and persistence of subsistence strategies, allowing inferences on the dramatic contraction (and extinction) of Fuegian populations.

  12. 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.

  13. Modeling the isotope effect in Walden inversion reactions

    Science.gov (United States)

    Schechter, Israel

    1991-05-01

    A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH 3T and CH 2TF from the reaction T + CH 3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    The atomic mass ratio of ca. 2 between deuterium and hydrogen is the highest for any pair of stable isotopes and results in significant and measurable H/D isotope effects in high temperature proton conductors containing these species. This paper discusses H/D isotope effects manifested in O......-H/O-D vibration frequencies, the mobility of H+/D+ carriers, the kinetics of the electrochemical oxidation of H2/D2, the solubilities of H2O/D2O and, finally, the spontaneous electromotive force that appears across H2/D2 cells with proton conducting electrolytes. Comparable work on tritium-exchanged materials...... is also discussed. The results highlight the usefulness of isotope effects in the study of high temperature proton conductors....

  15. Lead isotopic evidence for evolutionary changes in magma-crust interaction, Central Andes, southern Peru

    Energy Technology Data Exchange (ETDEWEB)

    Barreiro, B.A. (California Univ., Santa Barbara (USA). Dept. of Geological Sciences); Clark, A.H. (Queen' s Univ., Kingston, Ontario (Canada). Dept. of Geological Sciences)

    1984-07-01

    Lead isotopic measurements were made on Andean igneous rocks of Jurassic to Recent age in Moquegua and Tacna Departments, southernmost Peru, to clarify the petrogenesis of the rocks and, in particular, to investigate the effect of crustal thickness on rock composition. This location in the Cordillera Occidental is ideal for such a study because the ca. 2 Ga Precambrian basement rocks (Arequipa massif) have a distinct Pb isotopic signature which is an excellent tracer of crustal interaction, and because geomorphological research has shown that the continental crust was here thickened drastically in the later Tertiary.

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

    Science.gov (United States)

    Sharma, Sudhir C.; Klinman, Judith P.

    2009-01-01

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

  17. The Cl Isotope Composition of the Moon as evidence for an Anhydrous Mantle (Invited)

    Science.gov (United States)

    Sharp, Z. D.; Shearer, C., Jr.; McKeegan, K. D.; Barnes, J.; Wang, Y.

    2010-12-01

    The chlorine isotope composition of primitive terrestrial basalts and carbonaceous chondrites cover a narrow range centered around 0‰ with a total variation of ± 0.5‰. In contrast, the chlorine isotope composition of bulk samples and in situ ion microprobe analyses of lunar basalts and glasses cover a range of 25‰. Three possibilities were considered to explain the large spread: 1) initial isotopic heterogeneities, 2) devolatilization from solar wind/micrometeorite bombardment, 3) degassing under anhydrous conditions. The first of these possibilities is rejected because the Moon went through an magma ocean stage which would have homogenized any isotopic heterogeneities. To examine surface effects, we chose samples that have extremely different degrees of surface exposure. We find no correlation between the Cl isotope composition and surface exposure. We also conducted a laboratory experiment in which a thin film of NaCl was bombarded with a proton source for 24 hours with no change in Cl isotope composition. The third possibility is that the fractionation is explained by the anhydrous character of the Moon. On Earth, the volatiling Cl species is HCl. HCl is known to preferentially incorporate 37Cl relative to 35Cl due to the high bond strength of the molecule. This is offset by the higher translational velocity of H35Cl, so that overall, there is very little Cl isotope fractionation during degassing. We propose that lunar basalts were anhydrous and the volatile Cl species were metal chlorides, such as ZnCl2, NaCl, FeCl2, etc. The bond strength of metal chlorides and Cl dissolved in a basalt are similar, so that fractionation is caused mainly by volatilization, with the light isotopologue preferentially lost to the vapor phase. This idea is supported by the consistent lower Cl isotope ratios of water soluble salt fraction (~10 ‰ lower) and the lowest lunar Cl isotope values close to those of bulk Earth. The H content of lunar magmas must have been lower

  18. Stable isotope evidence for trophic niche partitioning in a South African savanna rodent community

    Institute of Scientific and Technical Information of China (English)

    Jacqueline CODRON; Kevin J DUFFY; Nico L AVENANT; Matt SPONHEIMER; Jennifer LEICHLITER; Oliver PAINE; Paul SANDBERG; Daryl CODRON

    2015-01-01

    Species’ partitioning of resources remains one of the most integral components for understanding community assem-bly. Analysis of stable carbon and nitrogen isotopes in animal tissues has the potential to help resolve patterns of partitioning be-cause these proxies represent the individual’s diet and trophic niche, respectively. Using free-ranging rodents in a southern Afri-can savanna as a model community, we find that syntopic species within habitats occupy distinct isotope niches. Moreover, spe-cies with strongly overlapping isotope niches did not overlap in their spatial distribution patterns, suggesting an underlying effect of competitive exclusion. Niche conservatism appears to characterize the behaviour of most species in our sample – with little or no observed changes across habitats – with the exception of one species,Mastomys coucha. This species displayed a generalist distribution, being found in similar abundances across a variety of habitats. This spatial pattern was coupled with a generalist isotope niche that shifted across habitats, likely in response to changes in species composition over the same spatial gradient. The case forM. coucha supports contentions that past competition effects played a significant evolutionary role in shaping community structures of today, including the absence of strong interspecific niche overlaps within particular habitats. Our study highlights the value of stable isotope approaches to help resolve key questions in community ecology, and moreover introduces novel ana-lytical approaches to quantifying isotope niche breadths and niche overlaps that are easily comparable with traditional metrices [Current Zoology 61 (3): 397–441, 2015].

  19. Isotope and density profile effects on pedestal neoclassical transport

    Science.gov (United States)

    Buller, S.; Pusztai, I.

    2017-10-01

    Cross-field neoclassical transport of heat, particles and momentum is studied in sharp density pedestals, with a focus on isotope and profile effects, using a radially global approach. Global effects—which tend to reduce the peak ion heat flux, and shift it outward—increase with isotope mass for fixed profiles. The heat flux reduction exhibits a saturation with a favorable isotopic trend. A significant part of the heat flux can be convective even in pure plasmas, unlike in the plasma core, and it is sensitive to how momentum sources are distributed between the various species. In particular, if only ion momentum sources are allowed, in global simulations of pure plasmas the ion particle flux remains close to its local value, while this may not be the case for simulations with isotope mixtures or electron momentum sources. The radial angular momentum transport that is a finite orbit width effect, is found to be strongly correlated with heat sources.

  20. Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments

    Science.gov (United States)

    Hu, Ningjing; Huang, Peng

    2016-04-01

    Anthropogenic Pb input into Bohai Bay, China: Evidence from stable Pb isotopic compositions in sediments Hu Ning-jinga, Huang Pengb,, Liu Ji-huaa, a First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China b Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China To investigate the source of Pb within Bohai Bay, Pb concentrations and Pb isotopic compositions (204Pb, 206Pb, 207Pb, and 208Pb) of surface sediments in this area were determined. The Pb concentration in this bay varied widely from 6.9 to 39.2 μg/g (average: 21.8 ± 7.8 μg/g), and the Pb isotopic compositions ranged from 0.8338 to 0.8864 (average: 2.0997 ± 0.0180) for 208Pb/206Pb and from 2.0797 to 2.1531 (average: 0.8477 ± 0.0135) for 207Pb/206Pb, presenting in three distinct clusters. The Pb isotopic ratios of sediments from the northeastern (NE zone) and northwestern (NW zone) coastal areas were significantly influenced by anthropogenic sources such as coal combustion and automobile emission. In sediments from the central and southern Bohai Bay (C-S zone); however, Pb mainly originated from the Yellow River catchment, as a result of lithogenic sediment (from rock weathering) accumulation. The Pb isotopic ratios further indicate that, apart from riverine inputs, the neighboring large-scale ports and aerosols significantly contributed to the anthropogenic Pb contained in these sediments. Pb contamination in the Haihe and Luanhe river mouths as well as in the regions near ports is also suggested from anthropogenic enrichment factors. As cities and ports continue to develop around Bohai Bay, a long-term extensive sewage monitoring program is highly recommended.

  1. Heat Capacity of PbS: Isotope Effects

    OpenAIRE

    Cardona, M.; Kremer, R. K.; Lauck, R.; Siegle, G.; Serrano, J.; Romero, A. H.

    2007-01-01

    In recent years, the availability of highly pure stable isotopes has made possible the investigation of the dependence of the physical properties of crystals, in particular semiconductors, on their isotopic composition. Following the investigation of the specific heat ($C_p$, $C_v$) of monatomic crystals such as diamond, silicon, and germanium, similar investigations have been undertaken for the tetrahedral diatomic systems ZnO and GaN (wurtzite structure), for which the effect of the mass of...

  2. Isotopic evidence of magmatism and a sedimentary carbon source at the Endeavour hydrothermal system

    Energy Technology Data Exchange (ETDEWEB)

    Brown, T A; Proskurowski, G; Lilley, M D

    2004-01-07

    Stable and radiocarbon isotope measurements made on CO{sub 2} from high temperature hydrothermal vents on the Endeavour Segment of the Juan de Fuca Ridge indicate both magmatic and sedimentary sources of carbon to the hydrothermal system. The Endeavour segment is devoid of overlying sediments and has shown no observable signs of surficial magmatic activity during the {approx}20 years of ongoing studies. The appearance of isotopically heavy, radiocarbon dead CO{sub 2} after a 1999 earthquake swarm requires that this earthquake event was magmatic in origin. Evidence for a sedimentary organic carbon source suggests the presence of buried sediments at the ridge axis. These findings, which represent the first temporally coherent set of radiocarbon measurements from hydrothermal vent fluids, demonstrate the utility of radiocarbon analysis in hydrothermal studies. The existence of a sediment source at Endeavour and the occurrence of magmatic episodes illustrate the extremely complex and evolving nature of the Endeavour hydrothermal system.

  3. ISOTOPIC REGIME OF SUBGLACIAL LAKE VOSTOK ON EVIDENCE FROM DEEP ICE CORE STUDIES

    Directory of Open Access Journals (Sweden)

    A. A. Ekaykin

    2012-01-01

    variability is observed here, which is attributed to the pulsations of the flux and/or isotope content of the melt glacier waters coming from the northern part of the lake. In turn, this means not complete mixing of the lake source waters with the resident water of the lake and, thus, that the water layer just beneath the glacier in the Vostok station area is not representative in terms of the conditions in the main lake body. We suggest that the future direct lake studies must include water sampling at different depths from the lake-water interface to the bottom. Meanwhile, in the nearest future this study will be developed by the completing of the measurements of the whole 5G-2 core (to the depth of3769 m, as well as the analysis of the short-term (1 cm variations in the bottom part of the ice core, where the isotopic signal must be fully preserved without being erased by the molecular diffusion. Also, the measurement of the first lake water sample recovered from the drill after the penetration will allow the comparison with the lake ice isotope content in order to experimentally define the effective isotope fractionation coefficient and thus constrain the possible mechanism of the lake ice formation.

  4. Lithium isotope effect accompanying electrochemical intercalation of lithium into graphite

    CERN Document Server

    Yanase, S; Oi, T

    2003-01-01

    Lithium has been electrochemically intercalated from a 1:2 (v/v) mixed solution of ethylene carbonate (EC) and methylethyl carbonate (MEC) containing 1 M LiClO sub 4 into graphite, and the lithium isotope fractionation accompanying the intercalation was observed. The lighter isotope was preferentially fractionated into graphite. The single-stage lithium isotope separation factor ranged from 1.007 to 1.025 at 25 C and depended little on the mole ratio of lithium to carbon of the lithium-graphite intercalation compounds (Li-GIC) formed. The separation factor increased with the relative content of lithium. This dependence seems consistent with the existence of an equilibrium isotope effect between the solvated lithium ion in the EC/MEC electrolyte solution and the lithium in graphite, and with the formation of a solid electrolyte interfaces on graphite at the early stage of intercalation. (orig.)

  5. Evidence for a catalytic six-membered cyclic transition state in aminolysis of 4-nitrophenyl 3,5-dinitrobenzoate in acetonitrile: comparative brønsted-type plot, entropy of activation, and deuterium kinetic isotope effects.

    Science.gov (United States)

    Um, Ik-Hwan; Kim, Min-Young; Bae, Ae-Ri; Dust, Julian M; Buncel, Erwin

    2015-01-02

    A kinetic study for reactions of 4-nitrophenyl 3,5-dinitrobenzoate (1a) with a series of cyclic secondary amines in acetonitrile is reported. Plots of the pseudo-first-order rate constant (kobsd) vs [amine] curve upward, while those of kobsd /[amine] vs [amine] exhibit excellent linear correlations with positive intercepts, indicating that the reaction proceeds through both uncatalyzed and catalyzed routes. Brønsted-type plots for uncatalyzed and catalyzed reactions are linear with βnuc = 1.03 and 0.69, respectively. The ΔH(⧧) and ΔS(⧧) values measured for the catalytic reaction with morpholine are -0.80 kcal/mol and -61.7 cal/(mol K), respectively. The negative ΔH(⧧) with a large negative ΔS(⧧) suggests that the reaction proceeds through a highly ordered transition state (i.e., a six-membered cyclic transition state, which includes a second amine molecule that accepts a proton from the aminium moiety of the zwitterionic tetrahedral intermediate and simultaneously donates a proton to the aryloxyl oxygen of the nucleofuge with concomitant C-OAr bond scission). This proposal is consistent with the smaller βnuc value for the catalyzed reaction as compared to the uncatalyzed reaction. An inverse deuterium kinetic isotope effect (DKIE) value of 0.93 and a contrasting normal primary DKIE value of 3.23 for the uncatalyzed and catalyzed routes, respectively, also support the proposed cyclic transition state.

  6. Secondary. beta. -deuterium isotope effects in decarboxylation and elimination reactions of. cap alpha. -lactylthiamin: intrinsic isotope effects of pyruvate decarboxylase

    Energy Technology Data Exchange (ETDEWEB)

    Kluger, R.; Brandl, M.

    1986-11-26

    The reactions of the adduct of pyruvate and thiamine, lactylthiamin (2-(lact-2-yl)thiamine), are accurate nonenzymic models for reactions of intermediates formed during catalysis by pyruvate decarboxylase. The enzymatic reaction generates lactylthiamin diphosphate from pyruvate and thiamine diphosphate. ..beta..-Deuterium isotope effects were determined for the nonenzymic reactions, and the results were related to isotope effects on the enzymic reaction. 2-(Lact-2-yl-..beta..-d/sub 3/) thiamine was prepared by condensation of methyl pyruvate-d/sub 3/ with thiamine followed by hydrolysis. The isotope effect for decarboxylation of lactylthiamin in acidic solution at 25/sup 0/C (k/sub H3//k/sub D3/) is 1.09 (standard deviation (SD) 0.015) in pH 3.8, 0.5 M sodium acetate: isotope effect = 1.095 (SD 0.014) in 0.001 M HCl. The reaction was also studied using 38% ethanolic aqueous sodium acetate (pH 3.8 before mixing with ethanol) since the enzymic sites are less polar than water and the reaction is significantly accelerated by the cosolvent. The isotope effect is within statistical range of that for the reaction in water, 1.105 (SD 0.016), indicating that acceleration by the solvent does not change the extent of hyperconjugative stabilization of the transition state relative to the ground state. The isotope effect for the base-catalyzed elimination of pyruvate from lactylthiamin was determined from kinetic studies by using multiwavelength analysis for reactions in pH 11 sodium carbonate solution. The isotope effect (k/sub H3//k/sub D3/) is 1.12 (SD 0.01), which is slightly higher than the effect on decarboxylation.

  7. 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.

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

    Directory of Open Access Journals (Sweden)

    J. C. Vogel

    1983-12-01

    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.

  9. Isotopic and physical evidence for persistently high eruption temperatures for Yellowstone-Snake River Plain rhyolites

    Science.gov (United States)

    Loewen, M.; Bindeman, I. N.; Melnik, O. E.

    2015-12-01

    Low crystallinity rhyolite lavas and tuffs from the Yellowstone-Snake River plain system were long-thought to erupt at high 800-900 °C temperatures with evidence derived from experimental work and geothermometry (e.g., QUILF, Ti-in-quartz). Despite this evidence, newer experimental phase equilibria studies as well as a reformulation of zircon saturation temperatures support lower temperature magma eruption conditions. Here we present two independent lines of evidence for 850 °C and greater temperatures. We present high precision oxygen isotope thermometry for coexisting quartz, glass, pyroxene, and magnetite in order make temperature estimates independent of phase equilibria. For all analyzed Snake River Plain-Yellowstone rhyolites, we determine 800-1100 °C temperatures for clinopyroxene and 850-1100 °C temperatures for magnetite. Extremely slow oxygen diffusion in pyroxene will preserve oxygen isotope crystal composition for millions of years stored at magmatic temperatures. Interestingly, oxygen in magnetite will reequilibrate in ice caps or prexisiting topography did not otherwise restrict flow. Using these results and simple conductive cooling models, we show that flows erupted at >800 °C and probably ~850 °C in order to be emplaced before cooling below the melt-glass transition and forming a more dome-like and lobate morphology.

  10. Uplift and submarine formation of some Melanesian porphyry copper deposits: Stable isotope evidence

    Science.gov (United States)

    Chivas, A.R.; O'Neil, J.R.; Katchan, G.

    1984-01-01

    Hydrogen and oxygen isotope analyses of sericites and kaolinites from four young porphyry copper deposits (Ok Tedi (1.2 Ma) and Yandera (6.5 Ma), Papua New Guinea; Koloula (1.5 Ma), Solomon Islands; and Waisoi (ocean water. For Ok Tedi, the non-magmatic component was a meteoric water with an isotopic composition different from that of the present meteoric water in the region. The isotopic signature of the former meteoric water is consistent with a surface elevation of 200 m a.s.l. or less at the time of mineralization. The deposit was later exposed and supergene kaolinitization commenced at approximately 1200 m a.s.l. Uplift and erosion has continued to the present at which time the elevation of the exposed deposit is 1800 m a.s.l. This rate of uplift is consistent with that known from other geological evidence. If the rate of uplift were approximately constant during the last 1.2 Ma, the age of supergene enrichment can be dated at approximately 0.4 Ma B.P. Similarly, influx of meteoric water at Yandera occurred when the ground surface above the deposit was at an elevation of approximately 600 m a.s.l. The deposit's present elevation is 1600 m a.s.l. In this case a total uplift of approximately 2.2 km is indicated, with removal of 1.2 km of overburden by erosion. ?? 1984.

  11. New isotopic evidence bearing on bonanza (Au-Ag) epithermal ore-forming processes

    Science.gov (United States)

    Saunders, James A.; Mathur, Ryan; Kamenov, George D.; Shimizu, Toru; Brueseke, Matthew E.

    2016-01-01

    New Cu, S, and Pb isotope data provide evidence for a magmatic source of metal(loid)s and sulfur in epithermal Au-Ag deposits even though their ore-forming solutions are composed primarily of heated meteoric (ground) waters. The apparent isotopic discrepancy between ore metals and ore-forming solutions, and even between the ore and associated gangue minerals, indicates two different sources of epithermal ore-forming constituents: (1) a shallow geothermal system that not only provides the bulk of water for the ore-forming solutions but also major chemical constituents leached from host rocks (silica, aluminum, potassium, sodium, calcium) to make gangue minerals and (2) metals and metalloids (As, Te, Sb, etc.) and sulfur (±Se) derived from deeper magma bodies. Isotopic data are consistent with either vapor-phase transport of metal(loids) and sulfur and their subsequent absorption by shallow geothermal waters or formation of metallic (Au, Ag, Cu phases) nanoparticles at depth from magmatic fluids prior to encountering the geothermal system. The latter is most consistent with ore textures that indicate physical transport and aggregation of nanoparticles were significant ore-forming processes. The recognition that epithermal Au-Ag ores form in tectonic settings that produce magmas capable of releasing metal-rich fluids necessary to form these deposits can refine exploration strategies that previously often have focused on locating fossil geothermal systems.

  12. 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

  13. Isotopic evidence for the source and fate of P in the Everglades wetlands

    Science.gov (United States)

    Li, X.; Wang, Y.

    2007-12-01

    High phosphorus (P) influx into wetland ecosystems in the Florida Everglades continues to be a problem. The increased P loading has been linked to changes in flora and fauna and the degradation of water quality in the wetlands. The number and species of animals have dramatically declined due to the agricultural and urban development since 1900. The plant community has also shifted from P-limited sawgrass (Cladium) to P-adapted cattail (Typha) in areas impacted by agricultural runoff. Although the effects of P loading on ecosystem have been recognized, little is known about how those changes affect the biogeochemical processes regulating P availability and cycling in freshwater ecosystems. The P-O bond in phosphate is resistant to hydrolysis in inorganic systems. However, the P-O bond can be easily broken in enzyme-mediated biochemical reactions, resulting in rapid oxygen isotope exchange with surrounding water within organisms. Thus, oxygen isotopic composition of phosphate should indicate the environment and processes of its formation. Oxygen isotopes in phosphate may provide a useful tool for tracing the source and recycling of phosphorus in aquatic systems. Here, I present the results of an oxygen isotopic study of phosphate in a constructed wetland (Storm water Treatment Area STA-1W) in northern Everglades as well as in a relatively pristine wetland in the Everglades National Park (ENP). Oxygen isotopic compositions of dissolved inorganic phosphate (DIP) in water and of total phosphate in sediment were determined using a High Temperature Conversion Elemental Analyzer (TC/EA) interfaced to a Finnigan MAT Delta Plus XP stable isotope ratio mass spectrometer (IRMS) at NHMFL. The data show: 1) there is no clear relationship between the d18O of DIP and P concentration in the water; 2) the d18O value of DIP is correlated with hydrological data (what kind?); 3) d18O value of DIP is not in equilibrium with water. The DIP samples collected in July are closer to isotopic

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

    Directory of Open Access Journals (Sweden)

    Nicolas Lecomte

    Full Text Available BACKGROUND: 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. METHODOLOGY/PRINCIPAL FINDINGS: 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. CONCLUSION/SIGNIFICANCE: 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

  15. Antiquity and evolutionary status of bacterial sulfate reduction: sulfur isotope evidence.

    Science.gov (United States)

    Schidlowski, M

    1979-09-01

    The presently available sedimentary sulfur isotope record for the Precambrian seems to allow the following conclusions: (1) In the Early Archaean, sedimentary delta 34S patterns attributable to bacteriogenic sulfate reduction are generally absent. In particular, the delta 34S spread observed in the Isua banded iron formation (3.7 x 10(9) yr) is extremely narrow and coincides completely with the respective spreads yielded by contemporaneous rocks of assumed mantle derivation. Incipient minor differentiation of the isotope pattersn notably of Archaean sulfates may be accounted for by photosynthetic sulfur bacteria rather than by sulfate reducers. (2) Isotopic evidence of dissimilatory sulfate reduction is first observed in the upper Archaean of the Aldan Shield, Siberia (approximately 3.0 x 10(9) yr) and in the Michipicoten and Woman River banded iron formations of Canada (2.75 x 10(9) yr). This narrows down the possible time of appearance of sulfate respirers to the interval 2.8--3.1 x 10(9) yr. (3) Various lines of evidence indicate that photosynthesis is older than sulfate respiration, the SO4(2-) Utilized by the first sulfate reducers deriving most probably from oxidation of reduced sulfur compounds by photosynthetic sulfur bacteria. Sulfate respiration must, in turn, have antedated oxygen respiration as O2-respiring multicellular eucaryotes appear late in the Precambrian. (4) With the bulk of sulfate in the Archaean oceans probably produced by photosynthetic sulfur bacteria, the accumulation of SO4(2-) in the ancient seas must have preceded the buildup of appreciable steady state levels of free oxygen. Hence, the occurrence of sulfate evaporites in Archaean sediments does not necessarily provide testimony of oxidation weathering on the ancient continents and, consequently, of the existence of an atmospheric oxygen reservoir.

  16. Boron isotope effect in superconducting MgB2.

    Science.gov (United States)

    Bud'ko, S L; Lapertot, G; Petrovic, C; Cunningham, C E; Anderson, N; Canfield, P C

    2001-02-26

    We report the preparation method of and boron isotope effect for MgB2, a new binary intermetallic superconductor with a remarkably high superconducting transition temperature T(c)(10B) = 40.2 K. Measurements of both temperature dependent magnetization and specific heat reveal a 1.0 K shift in T(c) between Mg11B2 and Mg10B2. Whereas such a high transition temperature might imply exotic coupling mechanisms, the boron isotope effect in MgB2 is consistent with the material being a phonon-mediated BCS superconductor.

  17. Microscale reservoir effects on microbial sulfur isotope fractionation

    Science.gov (United States)

    Louca, Stilianos; Crowe, Sean A.

    2017-04-01

    Microbial sulfate reduction can impart strong sulfur isotope fractionation by preferentially using the lighter 32SO42- over the heavier 34SO42-. The magnitude of fractionation depends on a number of factors, including ambient concentrations of sulfate and electron donors. Sulfur isotope compositions in sedimentary rocks thus facilitate reconstruction of past environmental conditions, such as seawater sulfate concentrations, primary productivity, organic carbon burial, and sulfur fluxes into or out of the ocean. Knowing the processes that regulate the magnitude of sulfur isotope fractionation is necessary for the correct interpretation of the geological record, but so far theoretical work has focused mostly on internal cellular processes. In sulfate-limited environments, like low sulfate lakes and the Archean ocean, microbial sulfate reduction can lead to sulfate depletion in the water column and an enrichment in isotopically heavy sulfate. This reservoir effect in turn mutes the fractionation expressed in the water column and ultimately preserved in sediments relative to the biologically induced fractionation. Here we use mathematical modeling to show that similar reservoir effects can also appear at the microscale in close proximity to sulfate-reducing cells. These microscale reservoir effects have the potential to modulate sulfur isotope fractionation to a considerable degree, especially at low (micromolar) sulfate concentrations. As a result, background sulfate concentrations, sulfate reduction rates, and extracellular ion diffusion rates can influence the fractionation expressed even if the physiologically induced fractionation is constant. This has implications for the interpretation of biogenic sulfur isotope fractionations expressed in the geological record, because the correct estimation of the environmental conditions that would promote these fractionations requires consideration of microscale reservoir effects. We discuss these implications, and

  18. Isotopic evidence in tree rings for historical changes in atmospheric sulfur sources.

    Science.gov (United States)

    Kawamura, Hidehisa; Matsuoka, Nobuaki; Momoshima, Noriyuki; Koike, Masami; Takashima, Yoshimasa

    2006-09-15

    Little is understood about the usefulness of sulfur isotopic ratios (sigma 34S) in tree rings because the sulfur content in rings is generally insufficient for analysis using conventional methods. We present sigma 34S values of the water-soluble and the organically bound sulfur fractions in rings of coniferous trees grown in Japan, analyzed using a large-volume oxygen bomb. Comparing the sigma 34S values of the organically bound fraction in tree rings with past atmospheric sulfur concentrations and with those of their sources, we find clear evidence that the sigma 34S values of the organically bound fraction in the rings are dependent upon the values of the atmospheric sulfur sources. The evidence suggests that the sigma 34S values in tree rings are a useful chronological proxy for evaluating possible causes of past atmospheric sulfur pollution.

  19. Saharan dust in Yucatan soils: Sr isotope and trace element evidence of dust inputs

    Science.gov (United States)

    Das, R.; Pett-Ridge, J. C.; D'Odorico, P.; Lawrence, D.

    2012-12-01

    Saharan dust transport is an important source of material for soil development in Caribbean islands, and may even be a larger source than the weathering of parent material on calcareous substrates in the Florida Keys and Bahamas. The Yucatan peninsula has similar soils and limestone parent materials, and receives annual Saharan dust inputs, but the importance of long-range dust transport for soil development in the region remains uncertain. Here we find evidence of Saharan dust in soils from a karst landscape in the central Yucatan peninsula using Sr isotopes, trace and rare earth element geochemistry. 87Sr/86Sr isotope ratios and trace element concentrations were measured in three soil profiles - an upland mature forest, upland secondary forest and depositional lowland (bajo) mature forest. 87Sr/86Sr isotope ratios in the upland mature and secondary forests were close to local limestone bedrock, while the bajo soil profile had higher values than local bedrock or Central American volcanic inputs, indicating the influence of Saharan dust. Trace element concentrations and rare earth element patterns in the upland mature forest and bajo profiles are more similar to values for Saharan dust and Central American volcanic sources than to local limestone bedrock. However, influence from volcanic sources would have lower 87Sr/86Sr values, indicating that Saharan dust influence is more likely. The bajo soil shows higher 87Sr/86Sr ratios and trace element concentrations compared to the upland soils, especially the secondary forest profile, indicating that soil disturbance and transport within the karst landscape influence the fate of eolian inputs and trace element geochemistry of soils in this region. Saharan dust is an important input to soil development at this location, and further work using isotopes and rare earth elements are necessary to quantify long-term dust inputs as a source material for soil development; Plot of Sr isotope ratio vs trace element (Zr/Y) ratio in

  20. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    Science.gov (United States)

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-05-20

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

  1. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE dehalogenation was investigated. Selective biotransformation reactions (i of tetrachloroethene (PCE to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii of TCE to cis-1,2-dichloroethene (cis-DCE in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were −19.0‰ ± 0.9‰ (PCE and −12.2‰ ± 1.0‰ (TCE (95% confidence intervals. Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (−5.0‰ ± 0.1‰ and TCE (−3.6‰ ± 0.2‰. In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by −16.3‰ ± 1.4‰ (standard error than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of −2.4‰ ± 0.3‰ and the product chloride an isotope effect of −6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals. A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect. These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition. This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I or single electron transfer as reductive dehalogenation mechanisms.

  2. 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

  3. Oxygen isotope evidence for orbital-scale glacio-eustasy during middle Paleozoic greenhouse climates

    Science.gov (United States)

    Theiling, B. P.; Elrick, M.

    2011-12-01

    Orbital-scale cycles (or parasequences) are pervasive throughout Phanerozoic and Precambrian marine deposits. Cycles deposited under cool (icehouse) conditions are commonly attributed to orbitally-driven glacio-eustasy whereas cycles forming during warm (greenhouse) climates, which lack direct evidence for glacial ice, are not well understood because autogenic and tectonic processes can often be eliminated. This study utilizes δ18O of marine apatite to explore whether orbital-scale glacio-eustasy controlled cycle formation during Paleozoic greenhouse time intervals. Stacked orbital-scale carbonate cycles within the Upper Silurian Henryhouse Formation of central Oklahoma and the Upper Devonian Devil's Gate Formation of central Nevada were sampled for conodont apatite. Both successions accumulated in shallow epicontinental seas on the flooded North American craton in southern tropical paleolatitudes. Subtidal cycles (2-7 m thick) at both locations are generally composed of deeper subtidal skeletal mudstone-wackestone that coarsen upward into shallow subtidal skeletal wackestone-packstone at cycle tops which show no evidence of subaerial exposure. Conodont δ18O values from the Silurian range from 15.8-19.5% and the Devonian from 16.3-19.0%. The majority of sampled Silurian and Devonian cycles record low δ18O values in the deepest water facies (during sea-level rise and highstand) and higher δ18O values in the shallowest water facies (during sea-level fall and lowstand). The magnitude of isotopic shift across individual cycles ranges from 2.2-3.1% for Silurian and ≤1.6% for Devonian cycles. If the intracycle isotopic shifts were due only to seawater temperature changes, then subtropical surface seawater temperature (SST) fluctuated between ~6-14°C during individual cycle formation. This magnitude of shift is greater than that recorded in the tropics since the Last Glacial Maximum, suggesting that the Silurian and Devonian isotopic shifts were not just the result

  4. 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.

  5. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-03-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive.

  6. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-01-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive. PMID:28262764

  7. Kinetic isotope effect studies on aspartate aminotransferase: Evidence for a concerted 1,3 prototropic shift mechanism for the cytoplasmic isozyme and L-aspartate and dichotomy in mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Julin, D.A.; Kirsch, J.F. (Univ. of California, Berkeley (USA))

    1989-05-02

    The C alpha primary hydrogen kinetic isotope effects (C alpha-KIEs) for the reaction of the cytoplasmic isozyme of aspartate aminotransferase (cAATase) with (alpha-2H)-L-aspartate are small and only slightly affected by deuterium oxide solvent (DV = 1.43 +/- 0.03 and DV/KAsp = 1.36 +/- 0.04 in H{sub 2}O; DV = 1.44 +/- 0.01 and DV/KAsp = 1.61 +/- 0.06 in D{sub 2}O). The D{sub 2}O solvent KIEs (SKIEs) are somewhat larger and are essentially independent of deuterium at C alpha (D{sub 2}OV = 2.21 +/- 0.07 and D{sub 2}OV/KAsp = 1.70 +/- 0.03 with ({alpha}-1H)-L-aspartate; D{sub 2}OV = 2.34 +/- 0.12 and D{sub 2}OV/KAsp = 1.82 +/- 0.06 with ({alpha}-2H)-L- aspartate). The C alpha-KIEs on V and on V/KAsp are independent of pH from pH 5.0 to pH 10.0. These results support a rate-determining concerted 1,3 prototropic shift mechanism by the multiple KIE criteria. The large C alpha-KIEs for the reaction of mitochondrial AATase (mAATase) with L-glutamate (DV = 1.88 +/- 0.13 and DV/KGlu = 3.80 +/- 0.43 in H{sub 2}O; DV = 1.57 +/- 0.05 and DV/KGlu = 4.21 +/- 0.19 in D{sub 2}O) coupled with the relatively small SKIEs (D{sub 2}OV = 1.58 +/- 0.04 and D{sub 2}OV/KGlu = 1.25 +/- 0.05 with ({alpha}-1H)-L-glutamate; D{sub 2}OV = 1.46 +/- 0.06 and D{sub 2}OV/KGlu = 1.16 +/- 0.05 with (alpha-2H)-L-glutamate) are most consistent with a two-step mechanism for the 1,3 prototropic shift for this isozyme-substrate pair.

  8. Source of arsenic-bearing pyrite in southwestern Vermont, USA: sulfur isotope evidence.

    Science.gov (United States)

    Mango, Helen; Ryan, Peter

    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(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.

  9. 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...

  10. Kinetic secondary deuterium isotope effects for substituted benzaldehyde cyanohydrin formation

    Energy Technology Data Exchange (ETDEWEB)

    Okano, V.; do Amaral, L.; Cordes, E.H.

    1976-07-07

    ..cap alpha.. secondary deuterium isotope effects have been measured for the observed rate constants for addition of cyanide ion to a series of substituted benzaldehydes in aqueous solution at 25/sup 0/C. Under the experimental conditions employed, these reactions did not proceed to completion, and the observed isotope effects were corrected to account for the influence of the reverse reaction employing measured equilibrium constants for cyanohydrin formation and previously determined secondary deuterium isotope effect for the equilibrium constant for 4-methoxybenzaldehyde cyanohydrin formation. In the four cases studied, values of k/sub D//k/sub H/ varied from 1.15 to 1.20, only slightly lower than the calculated maximal value for complete formation of the anionic tetrahedral species which is the immediate product of the rate-determining step, 1.21. A trend in isotope effect as a function of substrate reactivity could not be definitively established. The results suffice to establish that addition of cyanide to benzaldehydes proceeds via transition states in which rehybridization of carbonyl carbon to the tetrahedral geometry is nearly complete.

  11. Uranium isotope evidence for temporary ocean oxygenation in the aftermath of the Sturtian Snowball Earth

    Science.gov (United States)

    Lau, Kimberly V.; Macdonald, Francis A.; Maher, Kate; Payne, Jonathan L.

    2017-01-01

    The appearance and radiation of animals are commonly attributed to Neoproterozoic oceanic oxygenation, yet independent geochemical evidence for such an event remains equivocal. Strata deposited between the Sturtian and Marinoan Snowball Earth glaciations (660 to 640 Ma) contain the earliest animal biomarkers and possible body fossils. To quantify the extent of seafloor oxygenation during this critical interval, we present uranium isotope ratios (238U/235U denoted as δ238 U) from limestone of the Taishir Formation in Mongolia through two stratigraphic sections that are separated by ∼75 km within the same depositional basin. Above the Sturtian glacial deposits, through ∼150 m of stratigraphy, δ238 U compositions have a mean value of -0.47‰. This interval is followed by a ∼0.3‰ decrease in δ238 U, coincident with the Taishir negative carbon isotope excursion. Thereafter, δ238 U values remain relatively low until the erosional unconformity at the base of the Marinoan glacial deposits. Using a box model, we show that the best explanation for the higher δ238 U values of the post-Sturtian limestones is extensive-but temporary-oxygenation of the seafloor, and is inconsistent with a scenario involving only increased delivery of uranium to the oceans due to post-Snowball weathering. The decline in δ238 U in overlying strata, coincident with the Taishir negative δ13 C excursion, indicates a subsequent decrease in seafloor oxygenation. The U isotopic data, combined with modeling results, challenge the notion of a simple, unidirectional oxygenation of Neoproterozoic oceans.

  12. 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

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

    Science.gov (United States)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan A.; Wang, David T.; Johnson, Matthew S.; Ono, Shuhei

    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). The deviation from this relationship is 0.3‰ ± 1.2‰ and 3.5‰ ± 0.7‰ for OH and Cl oxidation, respectively. This is consistent with model calculations performed using quantum chemistry and transition state theory. The OH and Cl reactions enrich the residual methane in the clumped isotopologue in open system reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane, will only have a minor (∼0.3‰) impact on the clumped isotope signature (Δ13CH3D, measured as a deviation from a stochastic distribution of isotopes) of tropospheric methane. This paper shows that Δ13CH3D will provide constraints on methane source strengths, and predicts that Δ12CH2D2 can provide information on methane sink strengths.

  14. 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.

  15. Stable isotope evidence for an amphibious phase in early proboscidean evolution.

    Science.gov (United States)

    Liu, Alexander G S C; Seiffert, Erik R; Simons, Elwyn L

    2008-04-15

    The order Proboscidea includes extant elephants and their extinct relatives and is closely related to the aquatic sirenians (manatees and dugongs) and terrestrial hyracoids (hyraxes). Some analyses of embryological, morphological, and paleontological data suggest that proboscideans and sirenians shared an aquatic or semiaquatic common ancestor, but independent tests of this hypothesis have proven elusive. Here we test the hypothesis of an aquatic ancestry for advanced proboscideans by measuring delta(18)O in tooth enamel of two late Eocene proboscidean genera, Barytherium and Moeritherium, which are sister taxa of Oligocene-to-Recent proboscideans. The combination of low delta(18)O values and low delta(18)O standard deviations in Barytherium and Moeritherium matches the isotopic pattern seen in aquatic and semiaquatic mammals, and differs from that of terrestrial mammals. delta(13)C values of these early proboscideans suggest that both genera are likely to have consumed freshwater plants, although a component of C(3) terrestrial vegetation cannot be ruled out. The simplest explanation for the combined evidence from isotopes, dental functional morphology, and depositional environments is that Barytherium and Moeritherium were at least semiaquatic and lived in freshwater swamp or riverine environments, where they grazed on freshwater vegetation. These results lend new support to the hypothesis that Oligocene-to-Recent proboscideans are derived from amphibious ancestors.

  16. Presolar Grains from Novae: Evidence from Neon and Helium Isotopes in Comet Dust Collections

    CERN Document Server

    Pepin, Robert O; Gehrz, Robert D; Starrfield, Sumner; 10.1088/0004-637X/742/2/86

    2012-01-01

    Presolar grains in meteorites and interplanetary dust particles (IDPs) carry non-solar isotopic signatures pointing to origins in supernovae, giant stars, and possibly other stellar sources. There have been suggestions that some of these grains condensed in the ejecta of classical nova outbursts, but the evidence is ambiguous. We report neon and helium compositions in particles captured on stratospheric collectors flown to sample materials from comets 26P/Grigg-Skjellerup and 55P/Tempel-Tuttle that point to condensation of their gas carriers in the ejecta of a neon (ONe) nova. The absence of detectable 3He in these particles indicates space exposure to solar wind (SW) irradiation of a few decades at most, consistent with origins in cometary dust streams. Measured 4He/20Ne, 20Ne/22Ne, 21Ne/22Ne and 20Ne/21Ne isotope ratios, and a low upper limit on 3He/4He, are in accord with calculations of nucleosynthesis in neon nova outbursts. Of these, the uniquely low 4He/20Ne and high 20Ne/22Ne ratios are the most diagn...

  17. Molybdenum isotope evidence for widespread anoxia in mid-Proterozoic oceans.

    Science.gov (United States)

    Arnold, G L; Anbar, A D; Barling, J; Lyons, T W

    2004-04-02

    How much dissolved oxygen was present in the mid-Proterozoic oceans between 1.8 and 1.0 billion years ago is debated vigorously. One model argues for oxygenation of the oceans soon after the initial rise of atmospheric oxygen approximately 2.3 billion years ago. Recent evidence for H(2)S in some mid-Proterozoic marine basins suggests, however, that the deep ocean remained anoxic until much later. New molybdenum isotope data from modern and ancient sediments indicate expanded anoxia during the mid-Proterozoic compared to the present-day ocean. Consequently, oxygenation of the deep oceans may have lagged that of the atmosphere by over a billion years.

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

    Energy Technology Data Exchange (ETDEWEB)

    Depaolo, D.J.; Kyte, F.T.; Marshall, B.D.

    1983-09-01

    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.

  19. 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).

  20. 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.

  1. Kinetic isotope effects for fast deuterium and proton exchange rates.

    Science.gov (United States)

    Canet, Estel; Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey

    2016-04-21

    By monitoring the effect of deuterium decoupling on the decay of transverse (15)N magnetization in D-(15)N spin pairs during multiple-refocusing echo sequences, we have determined fast D-D exchange rates kD and compared them with fast H-H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.

  2. Ca, Sr, Mo and U isotopes evidence ocean acidification and deoxygenation during the Late Permian mass extinction

    Science.gov (United States)

    Silva-Tamayo, Juan Carlos; Payne, Jon; Wignall, Paul; Newton, Rob; Eisenhauer, Anton; Weyer, Stenfan; Neubert, Nadja; Lau, Kim; Maher, Kate; Paytan, Adina; Lehrmann, Dan; Altiner, Demir; Yu, Meiyi

    2014-05-01

    The most catastrophic extinction event in the history of animal life occurred at the end of the Permian Period, ca. 252 Mya. Ocean acidification and global oceanic euxinia have each been proposed as causes of this biotic crisis, but the magnitude and timing of change in global ocean chemistry remains poorly constrained. Here we use multiple isotope systems - Ca, Sr, Mo and U - measured from well dated Upper Permian- Lower Triassic sedimentary sections to better constrain the magnitude and timing of change in ocean chemistry and the effects of ocean acidification and de-oxygenation through this interval. All the investigated carbonate successions (Turkey, Italy and China) exhibit decreasing δ44/40Ca compositions, from ~-1.4‰ to -2.0‰ in the interval preceding the main extinction. These values remain low during most of the Griesbachian, to finally return to -1.4‰ in the middle Dienerian. The limestone succession from southern Turkey also displays a major decrease in the δ88/86Sr values from 0.45‰ to 0.3‰ before the extinction. These values remain low during the Griesbachian and finally increase to 0.55‰ by the middle Dienerian. The paired negative anomalies on the carbonate δ44/40Ca and δ88/86Sr suggest a decrease in the carbonate precipitation and thus an episode of ocean acidification coincident with the major biotic crisis. The Mo and U isotope records also exhibit significant rapid negative anomalies at the onset of the main extinction interval, suggesting rapid expansion of anoxic and euxinic marine bottom waters during the extinction interval. The rapidity of the isotope excursions in Mo and U suggests substantially reduced residence times of these elements in seawater relative to the modern, consistent with expectations for a time of widespread anoxia. The large C-isotope variability within Lower Triassic rocks, which is similar to that of the Lower-Middle Cambrian, may reflect biologically controlled perturbations of the oceanic carbon cycle

  3. 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

  4. Isotopic (Pb, Sr, Nd, C, O) evidence for plume-related sampling of an ancient, depleted mantle reservoir

    Science.gov (United States)

    Chen, Wei; Simonetti, Antonio

    2015-02-01

    The exact mantle source for carbonatite melts remains highly controversial. Despite their predominant occurrence within continental (lithospheric) domains, the radiogenic isotope data from young (oceanic island basalts (OIBs). This feature suggests an intimate petrogenetic relationship with asthenospheric mantle. New Pb, Sr, C, and O isotopic data are reported here for constituent minerals from the Oka carbonatite complex, which is associated with the Cretaceous Monteregian Igneous Province (MIP), northeastern North America. The Pb isotope data define linear arrays in Pb-Pb isotope diagrams, with the corresponding Sr isotope ratios being highly variable (0.70314-0.70343); both these features are consistent with open system behavior involving at least three distinct mantle reservoirs. Compared to the isotope composition of known mantle sources for OIBs and carbonatite occurrences worldwide, the least radiogenic 207Pb/204Pb (14.96 ± 0.07) and 208Pb/204Pb (37.29 ± 0.15) isotopic compositions relative to their corresponding 206Pb/204Pb ratios (18.86 ± 0.08) reported here are distinct, and indicate the involvement of an ancient depleted mantle (ADM) source. The extremely unradiogenic Pb isotope compositions necessitate U/Pb fractionation early in Earth's history (prior to 4.0 Ga ago) and growth via a multi-stage Pb evolution model. The combined stable (C and O) and radiogenic isotopic compositions effectively rule out crustal/lithosphere contamination during the petrogenetic history of the Oka complex. Instead, the isotopic variations reported here most likely result from the mixing of discrete, small volume partial melts derived from a heterogeneous plume source characterized by a mixed HIMU-EM1-ADM signature.

  5. 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.

  6. Evidence for in-situ methane production in ice based on anomalous isotope analyses

    Science.gov (United States)

    Sowers, T. A.; Priscu, J.

    2004-12-01

    the Sajama ice core from central Bolivia (18oS, 69oW, 6542masl), for example, were 1X-5X higher than contemporaneous values recorded in polar ice cores [Campen et al., 2003]. \\delta13CH4 values from five discrete depths were compared to corresponding measurements made on the Taylor Dome ice core and suggest the additional (in-situ) CH_{4} in the Sajama samples has an average isotopic composition of -63.2±2.8‰ . For reference, atmospheric δ ^{13}CH_{4} values range from -42 to -45/pm over this period. The Sajama isotope values are characteristic of methanogenic CH_{4} emitted from most terrestrial ecosystems. The second case study revolves around ice that was recovered from a perennially ice covered lake in the McMurdo Dry Valleys, Antarctica. Previous work on ice from Lake Bonney demonstrated a rich microbial consortium located ~2m below the surface [Priscu et al., 1998]. Methane isotope analyses were made on ice from this depth interval to identify the presence of microbially produced CH_{4}. δ ^{13}CH_{4} and δ DCH4 results suggest the CH4 arises from acetogenic CH4 production as opposed to CO2 reduction. Campen, R.K., T. Sowers, and R.B. Alley, Evidence of Microbial Consortia Metabolizing Within a Low-Latitude Mountain Glacier, Geology, 31 (No. 3), 231-234, 2003. Priscu, J.C., et al., Perennial Antarctic Lake Ice: An oasis for life in a polar desert, Science, 280, 2095-2098, 1998.

  7. 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.

  8. Isotope Effects in Low Energy Ion-Atom Collisions

    Energy Technology Data Exchange (ETDEWEB)

    Havener, Charles C [ORNL; Seely, D. G. [Albion College; Thomas, J. D. [University of Toledo, Toledo, OH; Kvale, Thomas Jay [University of Toledo, Toledo, OH

    2009-01-01

    Isotope effects for charge transfer processes have recently received increased attention. The ion-atom merged-beams apparatus at Oak Ridge National Laboratory is used to measure charge transfer for low energy collisions of multi-charged ions with H and D and is therefore well suited to investigate isotope effects. The apparatus has been relocated and upgraded to accept high velocity beams from the 250 kV High Voltage Platform at the Multi-Charged Ion Research Facility. The intense higher velocity multi-charged ion beams allow, for the first time, measurements with both H and D from keV/u down to meV/u collision energies in the center-of-mass frame. When charge transfer occurs at relatively large inter-nuclear distances (via radial couplings) the ion-induced dipole attraction can lead to trajectory effects, causing differences in the charge transfer cross sections for H and D. A strong isotope effect (nearly a factor of two) has been observed in the cross section for Si4+ + H(D) below 0.1 eV/u. However, little or no difference is observed for N2+ + H(D). Recently, strong effects have been predicted for the fundamental system He2+ + H(D,T) at collision energies below 200 eV/u where charge transfer occurs primarily through united-atom rotational coupling. We are currently exploring systems where rotational coupling is important and isotopic differences in the cross section can be observed.

  9. Submarine Hydrothermal Activity on the Aeolian Arc: New Evidence from Helium Isotopes

    Science.gov (United States)

    Lupton, J.; de Ronde, C.; Baker, E.; Sprovieri, M.; Bruno, P.; Italiano, F.; Walker, S.; Faure, K.; Leybourne, M.; Britten, K.; Greene, R.

    2008-12-01

    In November 2007 we conducted a water-column and seafloor mapping study of the submarine volcanoes of the Aeolian Arc in the southern Tyrrhenian Sea aboard the R/V Urania. A total of 26 CTD casts were completed, 13 vertical casts and 13 tows. In addition to in situ measurements of temperature, conductivity, pressure and suspended particles, we also collected discrete samples for helium isotopes, methane, and trace metals. The helium isotope ratio, which is known to be an unambiguous indicator of hydrothermal input, showed a clear excess above background at 5 out of the 10 submarine volcanoes surveyed. We found the strongest helium anomaly over Marsili seamount, where the 3He/4He ratio reached maximum values of δ3He = 23% at 610 m depth compared with background values of ~7%. We also found smaller but distinct δ3He anomalies over Enerato, Eolo, Palinuro, and Secca del Capo. We interpret these results as indicating the presence of hydrothermal activity on these 5 seamounts. Hydrothermal venting has been documented at subsea vents offshore of the islands of Panarea, Stromboli, and Vulcano (Dando et al., 1999; Di Roberto et al., 2008), and hydrothermal deposits have been sampled on many of the submarine volcanoes of the Aeolian Arc (Dekov and Savelli, 2004). However, as far as we know this is the first evidence of present day hydrothermal activity on Marsili, Enerato, and Eolo. Samples collected over Filicudi, Glabro, Lamentini, Sisifo, and Alcioni had δ3He very close to the regional background values, suggesting either absence of or very weak hydrothermal activity on these seamounts. Helium isotope measurements from the background hydrocasts positioned between the volcanoes revealed the presence of an excess in 3He throughout the SE Tyrrhenian Sea. These background profiles reach a consistent maximum of about δ3He = 11% at 2300 m depth. Historical helium profiles collected in the central and northern Tyrrhenian Sea in 1987 and 1997 do not show this deep 3He

  10. 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.

  11. Identification of groundwater nitrate contamination from explosives used in road construction: Isotopic, chemical, and hydrologic evidence

    Science.gov (United States)

    Degnan, James R.; Böhlke, John Karl; Pelham, Krystle; David M. Langlais,; Walsh, Gregory J.

    2015-01-01

    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 δ15N, high δ18O) from dissolution of unexploded NH4NO3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO3– subjected to partial denitrification (high δ15N, high δ18O); (3) relatively persistent concentrations of blasting-related biogenic NO3– derived from nitrification of NH4+ (low δ15N, low δ18O); and (4) stable but spatially variable biogenic NO3– concentrations, consistent with recharge from septic systems (high δ15N, low δ18O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N2) and isotopic fractionation trends associated with denitrification (Δδ15N/Δδ18O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

  12. 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.

  13. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Salamalikis, V., E-mail: vsalamalik@upatras.gr [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Argiriou, A.A. [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Dotsika, E. [Stable Isotope Unit, Institute of Nanoscience and Nanotechnology, National Center of Scientific Research ‘Demokritos’, Ag. Paraskevi Attikis, 15310 Athens (Greece)

    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{sup 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

  15. Anharmonic phonons and the isotope effect in superconductivity

    Energy Technology Data Exchange (ETDEWEB)

    Crespi, V.H.; Cohen, M.L. (Department of Physics, University of California at Berkeley, Berkeley, CA (USA) Materials Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA (USA)); Penn, D.R. (National Institute of Standards and Technology, Gaithersburg, MD (USA))

    1991-06-01

    Anharmonic interionic potentials are examined in an Einstein model to study the unusual isotope-effect exponents for the high-{ital T}{sub {ital c}} oxides. The mass dependences of the electron-phonon coupling constant {lambda} and the average phonon frequency {radical}{l angle}{omega}{sup 2}{r angle} are computed from weighted sums over the oscillator levels. The isotope-effect exponent is depressed below 1/2 by either a double-well potential or a potential with positive quadratic and quartic parts. Numerical solutions of Schroedinger's equation for double-well potentials produce {lambda}'s in the range 1.5--4 for a material with a vanishing isotope-effect parameter {alpha}. However, low phonon frequencies limit {ital T}{sub {ital c}} to roughly 15 K. A negative quartic perturbation to a harmonic well can increase {alpha} above 1/2. In the extreme-strong-coupling limit, {alpha} is 1/2, regardless of anharmonicity.

  16. STABLE CARBON ISOTOPES OF HCO//3 IN THE AQUIA AQUIFER, MARYLAND: EVIDENCE FOR AN ISOTOPICALLY HEAVY SOURCE OF CO//2.

    Science.gov (United States)

    Chapelle, Francis H.; Knobel, LeRoy L.

    1985-01-01

    Identifying sources and sinks of dissolved inorganic carbon species is an important step in understanding the geochemistry of ground-water systems. This is particularly important for Atlantic Coastal Plain aquifers because bicarbonate (HCO//3** minus ) is frequently the major dissolved anion. The purpose of this paper is to document the stable carbon isotope composition of dissolved inorganic carbon in the Aquia aquifer, Maryland, and to use this data to help identify sources and sinks of dissolved HCO//3** minus . Subjects covered include hydrogeology, ground-water chemistry, sources and sinks, and others. Refs.

  17. Effect of interband interaction on isotope effect exponent of MgB2 superconductors

    Indian Academy of Sciences (India)

    P Udomsamuthirun; C Kumvongsa; A Burakorn; P Changkanarth

    2006-03-01

    The exact formula of c'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 interactions: the electron-phonon interaction and non-electron-phonon interaction. We find that the isotope effect exponent of MgB2, = 0.3 with c ≈ 40 K can be found in the weak coupling regime and interband interaction of electron-phonon shows more effect on the isotope effect exponent than on the interband interaction of non-phonon.

  18. Interaction of surface water and groundwater in the Nile River basin: isotopic and piezometric evidence

    Science.gov (United States)

    Kebede, Seifu; Abdalla, Osman; Sefelnasr, Ahmed; Tindimugaya, Callist; Mustafa, Osman

    2016-12-01

    Past discussions around water-resources management and development in the River Nile basin disregard groundwater resources from the equation. There is an increasing interest around factoring the groundwater resources as an integral part of the Nile Basin water resources. This is hampered by knowledge gap regarding the groundwater resources dynamics (recharge, storage, flow, quality, surface-water/groundwater interaction) at basin scale. This report provides a comprehensive analysis of the state of surface-water/groundwater interaction from the headwater to the Nile Delta region. Piezometric and isotopic (δ18O, δ2H) evidence reveal that the Nile changes from a gaining stream in the headwater regions to mostly a loosing stream in the arid lowlands of Sudan and Egypt. Specific zones of Nile water leakage to the adjacent aquifers is mapped using the two sources of evidence. Up to 50% of the surface-water flow in the equatorial region of the Nile comes from groundwater as base flow. The evidence also shows that the natural direction and rate of surface-water/groundwater interaction is largely perturbed by human activities (diversion, dam construction) particularly downstream of the Aswan High Dam in Egypt. The decrease in discharge of the Nile River along its course is attributed to leakage to the aquifers as well as to evaporative water loss from the river channel. The surface-water/groundwater interaction occurring along the Nile River and its sensitivity to infrastructure development calls for management strategies that account groundwater as an integral part of the Nile Basin resources.

  19. Interaction of surface water and groundwater in the Nile River basin: isotopic and piezometric evidence

    Science.gov (United States)

    Kebede, Seifu; Abdalla, Osman; Sefelnasr, Ahmed; Tindimugaya, Callist; Mustafa, Osman

    2017-05-01

    Past discussions around water-resources management and development in the River Nile basin disregard groundwater resources from the equation. There is an increasing interest around factoring the groundwater resources as an integral part of the Nile Basin water resources. This is hampered by knowledge gap regarding the groundwater resources dynamics (recharge, storage, flow, quality, surface-water/groundwater interaction) at basin scale. This report provides a comprehensive analysis of the state of surface-water/groundwater interaction from the headwater to the Nile Delta region. Piezometric and isotopic (δ18O, δ2H) evidence reveal that the Nile changes from a gaining stream in the headwater regions to mostly a loosing stream in the arid lowlands of Sudan and Egypt. Specific zones of Nile water leakage to the adjacent aquifers is mapped using the two sources of evidence. Up to 50% of the surface-water flow in the equatorial region of the Nile comes from groundwater as base flow. The evidence also shows that the natural direction and rate of surface-water/groundwater interaction is largely perturbed by human activities (diversion, dam construction) particularly downstream of the Aswan High Dam in Egypt. The decrease in discharge of the Nile River along its course is attributed to leakage to the aquifers as well as to evaporative water loss from the river channel. The surface-water/groundwater interaction occurring along the Nile River and its sensitivity to infrastructure development calls for management strategies that account groundwater as an integral part of the Nile Basin resources.

  20. Probing isotope effects in chemical reactions using single ions

    CERN Document Server

    Staanum, Peter F; Wester, Roland; Drewsen, Michael

    2008-01-01

    Isotope effects in reactions between Mg+ in the 3p 2P3/2 excited state and molecular hydrogen at thermal energies are studied through single reaction events. From only ~250 reactions with HD, the branching ratio between formation of MgD+ and MgH+ is found to be larger than 5. From additional 65 reactions with H2 and D2 we find that the overall decay probability of the intermediate MgH2+, MgHD+ or MgD2+ complexes is the same. Our study shows that few single ion reactions can provide quantitative information on ion-neutral reactions. Hence, the method is well-suited for reaction studies involving rare species, e.g., rare isotopes or short-lived unstable elements.

  1. 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

  2. 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....... But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle....

  3. Evidence of fissiogenic Cs estimated from Ba isotopic deviations in an Oklo natural reactor zone

    Science.gov (United States)

    Hidaka, Hiroshi; Holliger, Philippe; Masuda, Akimasa

    1993-01-01

    Isotopic studies of many elements from the uranium ore natural nuclear reactors at Oklo provide useful information on the migration of radioactive nuclides. The fissiogenic isotopic composition of Ba is particularly interesting, as it is an important indication in the search for fissiogenic Cs. In this report we detail the detection of remarkable isotopic deviations of Ba in the Oklo samples and estimate the geochemical behaviour of fissiogenic Cs from excess Ba isotopes. Six samples systematically collected from borehole SF84 (zone 10) at the Oklo uranium mine have been analyzed. Isotopic deviations of Ba indicate the existence of fissiogenic Cs and Ba. A good correlation between the elemental abundance of Cs and isotopic abundances of excess 135Ba and 137Ba suggests that fissiogenic 135Ba and 137Ba behaved as Cs rather than Ba.

  4. Stable isotope evidence for crustal recycling as recorded by superdeep diamonds

    OpenAIRE

    Burnham, A. D.; Thomson, A. R.; Bulanova, G. P.; Kohn, S. C.; Smith, C B; Walter, M. J.

    2015-01-01

    © 2015 Elsevier B.V. Sub-lithospheric diamonds from the Juina-5 and Collier-4 kimberlites and the Machado River alluvial deposit in Brazil have carbon isotopic compositions that co-vary with the oxygen isotopic compositions of their inclusions, which implies that they formed by a mixing process. The proposed model for this mixing process, based on interaction of slab-derived carbonate melt with reduced (carbide- or metal-bearing) ambient mantle, explains these isotopic observations. It is als...

  5. Evidence from stable isotopes and (10)Be 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.

  6. 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.

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

    CERN Document Server

    Banerjee, Projjwal; Heger, Alexander; Haxton, W C

    2016-01-01

    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 Be-10 can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed.

  8. Isotopic evidence on multiple sources of nitrogen in the northern Jiulong River, Southeast China

    Science.gov (United States)

    Cao, Wenzhi; Huang, Zheng; Zhai, Weidong; Li, Ying; Hong, Huasheng

    2015-09-01

    Riverine export accounts for a large portion of estuarine and coastal nutrients and could lead to severe eutrophication. However, nitrogen (N) sources at the catchment scale remain unclear because of spatial and temporal variations. The stable isotope of 15N, which has been proven to be effective in deducing sources and testing biogeochemical behaviours, is applied in this study to explore multiple sources of riverine N and their nutrient concentrations in the northern section of Jiulong River catchment seasonally. Results show that drastic seasonal variation in external nitrate sources occurs in the river; manure and sewage dominate during base flows, whereas organic N in soil and atmospheric deposition dominate during storm flows. The external sources change throughout the year depending on the environmental conditions. Furthermore, riverine nitrate import in the northern Jiulong River is dominated by an external process because of the increasing NO3- - δ15N value accompanied by an increasing NO3- -N concentration (p management and eutrophication reversal.

  9. Isotopic and elemental evidence for Scabland Flood sediments offshore Vancouver Island

    Science.gov (United States)

    Gombiner, Joel H.; Hemming, Sidney R.; Hendy, Ingrid L.; Bryce, Julia G.; Blichert-Toft, Janne

    2016-05-01

    Geological records contain evidence for catastrophic ice-sheet processes such as megafloods and massive ice discharges. Such large-scale phenomena, associated with ice sheet collapse, rapid sea-level rise, and disruptions to ocean circulation, have never been directly observed, but are forecast as a consequence of global warming. Here we use potassium-argon (K/Ar) ages and neodymium (Nd) isotopes as provenance tools to show that cyclical megafloods from the Cordilleran Ice Sheet of western North America traveled through the Channeled Scabland of Washington and transported sediments to the continental slope of Vancouver Island during the last glacial, laying down a sequence of rhythmically bedded sediments in deep-sea core MD02-2496. This work addresses longstanding questions about the absolute timing of Scabland Floods, their cyclicity, and the fate of their sediments and freshwater in the marine realm. Our data suggest that, between ˜19.3 and ˜14.9 ka, Scabland Floods repeatedly generated far-traveled sediment-water plumes in the NE Pacific Ocean, requiring a hydrologically active ice sheet system capable of producing catastrophic megafloods for about 4500 years.

  10. Desertification of the eastern Karoo, South Africa: Conflicting paleoecological, historical, and soil isotopic evidence.

    Science.gov (United States)

    Hoffman, M T; Bond, W J; Stock, W D

    1995-01-01

    The desertification debate in South Africa has benefitted greatly in recent years from the contributions of a wide range of disciplines. In this paper we review the conflicting and supporting evidence for degradation in the eastern Karoo as reported in recent archaeological, historical, and stable carbon isotope studies as it relates to three key aspects of the debate: the precolonial environment, the rate and nature of change, and the relative contributions of humans and climate to the process. First, all studies suggest a greater grassiness at some time in the past, but researchers disagree on the timing of the switch to more shrubby conditions in the eastern Karoo. Second, regional rainfall records for the past 2 decades reveal an above-average rainfall period, and numerous long-term surveys show an increase in grass cover over the same period. These findings question the expanding Karoo hypothesis as well as the argument that the Karoo's carrying capacity has decreased in recent years. Finally, the relative responsibilities of humans and climate in the degradation process remain poorly understood and generally have not formed the focus of investigation.

  11. Mesoproterozoic graphite deposits, New Jersey Highlands: Geologic and stable isotopic evidence for possible algal origins

    Science.gov (United States)

    Volkert, R.A.

    2000-01-01

    Graphite deposits of Mesoproterozoic age are locally abundant in the eastern New Jersey Highlands, where they are hosted by sulphidic biotite-quartz-feldspar gneiss, metaquartzite, and anatectic pegmatite. Gneiss and metaquartzite represent a shallow marine shelf sequence of locally organic-rich sand and mud. Graphite from massive deposits within metaquartzite yielded ??13C values of -26 ?? 2??? (1??), and graphite from massive deposits within biotite-quartz-feldspar gneiss yielded ??13C values of -23 ??4???. Disseminated graphite from biotite-quartz-feldspar gneiss country rock was -22 ??3???, indistinguishable from the massive deposits hosted by the same lithology. Anatectic pegmatite is graphitic only where generated from graphite-bearing host rocks; one sample gave a ??13C value of -15???. The ??34S values of trace pyrrhotite are uniform within individual deposits, but vary from 0 to 9??? from one deposit to another. Apart from pegmatitic occurrences, evidence is lacking for long-range mobilization of carbon during Grenvillian orogenesis or post-Grenvillian tectonism. The field, petrographic, and isotope data suggest that massive graphite was formed by granulite-facies metamorphism of Proterozoic accumulations of sedimentary organic matter, possibly algal mats. Preservation of these accumulations in the sedimentary environment requires anoxic basin waters or rapid burial. Anoxia would also favour the accumulation of dissolved ferrous iron in basin waters, which may explain some of the metasediment-hosted massive magnetite deposits in the New Jersey Highlands. ?? 2000 NRC.

  12. Evidence for free oxygen in the Neoarchean ocean based on coupled iron-molybdenum isotope fractionation

    Science.gov (United States)

    Czaja, Andrew D.; Johnson, Clark M.; Roden, Eric E.; Beard, Brian L.; Voegelin, Andrea R.; Nägler, Thomas F.; Beukes, Nicolas J.; Wille, Martin

    2012-06-01

    Most geochemical proxies and models of atmospheric evolution suggest that the amount of free O2 in Earth’s atmosphere stayed below 10-5 present atmospheric level (PAL) until the Great Oxidation Event (GOE) that occurred between ∼2.2 and 2.4 Ga, at which time free O2 in the atmosphere increased to approximately 10-1 to 10-2 PAL. Although photosynthetically produced “O2 oases” have been proposed for the photic zone of the oceans prior to the GOE, it has been difficult to constrain absolute O2 concentrations and fluxes in such paleoenvironments. Here we constrain free O2 levels in the photic zone of a Late Archean marine basin by the combined use of Fe and Mo isotope systematics of Ca-Mg carbonates and shales from the 2.68 to 2.50 Ga Campbellrand-Malmani carbonate platform of the Kaapvaal Craton in South Africa. Correlated Fe and Mo isotope compositions require a key role for Fe oxide precipitation via oxidation of aqueous Fe(II) by photosynthetically-derived O2, followed by sorption of aqueous Mo to the newly formed Fe oxides. A dispersion/reaction model illustrates the effects of Fe oxide production and Mo sorption to Fe oxides, and suggests that a few to a few tens of μM free O2 was available in the photic zone of the Late Archean marine basin, consistent with some previous estimates. The coupling of Fe and Mo isotope systematics provides a unique view into the processes that occurred in the ancient shallow ocean after production of free O2 began, but prior to oxygenation of the deep ocean, or significant accumulation of free O2 in the atmosphere. These results require oxygenic photosynthesis to have evolved by at least 2.7 Ga and suggest that the Neoarchean ocean may have had a different oxygenation history than that of the atmosphere. The data also suggest that the extensive iron formation deposition that occurred during this time was unlikely to have been produced by anoxygenic photosynthetic Fe(II) oxidation. Finally, these data indicate that the ocean

  13. Effective boson number calculations in Mo and Cd isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Cata, G.; Bucurescu, D.; Cutoiu, D.; Ivascu, M.; Zamfir, N.V. (Institutul Central de Fizica, Bucharest (Romania))

    1990-03-01

    The effects of the neutron-proton interaction on the low-lying levels of Mo and Cd isotopes have been considered in the frame of the IBA-1 model by taking into account an effective boson number (N{sub eff}). Both an empirical procedure based on previous IBA-2 mixing calculations and the N{sub p}N{sub n} scheme provide comparable N{sub eff} values. Level spectra and electromagnetic transitions are investigated. The results support the idea that IBA-1 calculations with a suitable N{sub eff} can largely simulate IBA-2 mixing calculations, taking advantage of simplicity and a smaller number of parameters. (orig.).

  14. Isotopic evidence that dragonflies (Pantala flavescens migrating through the Maldives come from the northern Indian subcontinent.

    Directory of Open Access Journals (Sweden)

    Keith A Hobson

    Full Text Available Large numbers of the Globe Skimmer dragonfly (Pantala flavescens appear in the Maldives every October-December. Since they cannot breed on these largely waterless islands, it has recently been suggested that they are "falling out" during a trans-oceanic flight from India to East Africa. In addition, it has been suggested that this trans-oceanic crossing is just one leg of a multi-generational migratory circuit covering about 14,000-18,000 km. The dragonflies are presumed to accomplish this remarkable feat by riding high-altitude winds associated with the Inter-tropical Convergence Zone (ITCZ. While there is considerable evidence for this migratory circuit, much of that evidence is circumstantial. Recent developments in the application of stable isotope analyses to track migratory dragonflies include the establishment of direct associations between dragonfly wing chitin δ(2H values with those derived from long-term δ(2H precipitation isoscapes. We applied this approach by measuring wing chitin δ(2H values in 49 individual Pantala flavescens from the November-December migration through the Maldives. Using a previously established spatial calibration algorithm for dragonflies, the mean wing δ(2H value of -117±16 ‰ corresponded to a predicted mean natal ambient water source of -81 ‰, which resulted in a probabilistic origin of northern India, and possibly further north and east. This strongly suggests that the migratory circuit of this species in this region is longer than previously suspected, and could possibly involve a remarkable trans-Himalayan high-altitude traverse.

  15. Isotopic evidence that dragonflies (Pantala flavescens) migrating through the Maldives come from the northern Indian subcontinent.

    Science.gov (United States)

    Hobson, Keith A; Anderson, R Charles; Soto, David X; Wassenaar, Leonard I

    2012-01-01

    Large numbers of the Globe Skimmer dragonfly (Pantala flavescens) appear in the Maldives every October-December. Since they cannot breed on these largely waterless islands, it has recently been suggested that they are "falling out" during a trans-oceanic flight from India to East Africa. In addition, it has been suggested that this trans-oceanic crossing is just one leg of a multi-generational migratory circuit covering about 14,000-18,000 km. The dragonflies are presumed to accomplish this remarkable feat by riding high-altitude winds associated with the Inter-tropical Convergence Zone (ITCZ). While there is considerable evidence for this migratory circuit, much of that evidence is circumstantial. Recent developments in the application of stable isotope analyses to track migratory dragonflies include the establishment of direct associations between dragonfly wing chitin δ(2)H values with those derived from long-term δ(2)H precipitation isoscapes. We applied this approach by measuring wing chitin δ(2)H values in 49 individual Pantala flavescens from the November-December migration through the Maldives. Using a previously established spatial calibration algorithm for dragonflies, the mean wing δ(2)H value of -117±16 ‰ corresponded to a predicted mean natal ambient water source of -81 ‰, which resulted in a probabilistic origin of northern India, and possibly further north and east. This strongly suggests that the migratory circuit of this species in this region is longer than previously suspected, and could possibly involve a remarkable trans-Himalayan high-altitude traverse.

  16. Tracing the Sources and Processes of Groundwater in an Alpine Glacierized Region in Southwest China: Evidence from Environmental Isotopes

    Directory of Open Access Journals (Sweden)

    Yuchuan Meng

    2015-05-01

    Full Text Available The melting of alpine snow and glaciers is an important hydrologic process on Mount Gongga, China. The relevance of ice-snow melt to the groundwater recharge in the glacierized Hailuogou watershed is so far not well known. To better understand the origin of groundwater and the hydrological interactions between groundwater, meltwater, and precipitation in this region, 148 environmental isotopic data of water samples were analyzed for changes in isotopic composition. The results indicate that the groundwater contains a uniform isotopic signature, with δ18O values between −13.5‰ and −11.1‰ and δ2H values between −90‰ and −75‰. The mean stable isotopic composition of groundwater is heavier than that of ice-snow meltwater but lighter than that of precipitation. The effect of evaporation on the isotopic variation of groundwater is very limited and the seasonal isotope variations in precipitation are attenuated in groundwater. A model based on the δ18O results suggests that approximately 35% of the groundwater is derived from ice-snow meltwater sources. The study demonstrates that ice-snow meltwater is a substantial source of shallow groundwater in the alpine regions on the edge of the Tibetan Plateau.

  17. Pb isotope evidence for contributions from different Iceland mantle components to Palaeogene East Greenland flood basalts

    DEFF Research Database (Denmark)

    Peate, David; Stecher, Ole

    2003-01-01

    We present new Pb isotope data on 21 samples of break-up-related flood basalts (56–54 Ma) from the Blosseville Kyst region of East Greenland. These samples show a considerable range in isotopic composition (206Pb/204Pb 17.6 to 19.3) that broadly correlates with compositional type. The ‘low-Ti’ type...

  18. Uranium Isotope Evidence for Temporary Ocean Oxygenation Following the Sturtian Glaciation

    Science.gov (United States)

    Lau, K. V.; Maher, K.; Macdonald, F. A.; Payne, J.

    2015-12-01

    The link between widespread ocean oxygenation in the Neoproterozoic and the rise of animals has long been debated, largely because the timing and nature of oxygenation of the oceans remain poorly constrained. Strata deposited during the Cryogenian non-glacial interlude (660 to 635 Ma), between the Sturtian and Marinoan Snowball Earth glaciations, contain the earliest fossil evidence of animals. To quantitatively estimate patterns of seafloor oxygenation during this critical interval, we present uranium isotope (δ238U) data from limestone of the Taishir Formation (Fm) in Mongolia in two stratigraphic sections that are separated by ~75 km across the basin. The Taishir Fm hosts two large δ13C excursions that co-vary in total organic and inorganic (carbonate) carbon: a basal carbonate δ13C excursion to -4‰ in the Sturtian cap carbonate, followed by a rise to enriched values of +8‰, a second negative δ13C excursion to -7‰ referred to as the Taishir excursion, followed by a second rise to +10‰. Above the Sturtian glacial deposits, in the stratigraphic interval below the Taishir excursion, δ238U compositions have a mean value that is similar to that of modern seawater. After the Taishir excursion, the δ238U record exhibits a step decrease of ~0.3‰, and δ238U remains approximately constant until the erosional unconformity at the base of the Marinoan glacial deposits. We use a box model to constrain the uranium cycle behavior that best explains our observations. In the model, the best explanation for the less negative post-Sturtian values of δ238U is extensive oxygenation of the seafloor. Moreover, the model demonstrates that the higher δ238U values of the post-Sturtian limestones are inconsistent with an increased flux of uranium to the oceans due to post-Snowball weathering as the primary driver of the excursion. Thus, we favor a scenario in which there was a rise in oxygen levels following the Sturtian glaciation followed by a decrease in seafloor

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

    Science.gov (United States)

    Burns, Douglas A.; Boyer, E.W.; Elliott, E.M.; Kendall, C.

    2009-01-01

    Knowledge of key sources and biogeochemical processes that affect the transport of nitrate (NO3-) in streams can inform watershed management strategies for controlling downstream eutrophication. We applied dual isotope analysis of NO3- to determine the dominant sources and processes that affect NO3- 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 NO3- concentrations, ?? 15NNO3, and ??18ONO3. Samples from two forested watersheds indicated that NO3- derived from nitrification was dominant at baseflow. A watershed dominated by suburban land use had three ??18ONO3 values greater than +25???, 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 ??15NNO3 values greater than +9???, suggesting an animal waste source consistent with regional dairy farming practices. These data showed a linear seasonal pattern with a ??18O NO3:??15NNO3 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 ?? 15NNO3 values (10???) 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 km2 may be necessary to adequately quantify the relative roles of various NO 3- transport and process patterns that contribute to streamflow in large basins. Copyright ?? 2009 by the American Society of

  20. Diets and environments of late Cenozoic mammals in the Qaidam Basin, Tibetan Plateau: Evidence from stable isotopes

    Science.gov (United States)

    Zhang, Chunfu; Wang, Yang; Li, Qiang; Wang, Xiaoming; Deng, Tao; Tseng, Zhijie J.; Takeuchi, Gary T.; Xie, Gangpu; Xu, Yingfeng

    2012-06-01

    The timing history and driving mechanisms of C4 expansion and Tibetan uplift are hotly debated issues. Paleoenvironmental evidence from within the Tibetan Plateau is essential to help resolve these issues. Here we report results of stable C and O isotope analyses of tooth enamel samples from a variety of late Cenozoic mammals, including deer, giraffe, horse, rhino, and elephant, from the Qaidam Basin in the northeastern Tibetan Plateau. The enamel-δ13C values are <-8‰ for modern samples and ≤-7‰ for fossils, except for one late Miocene rhino (CD0722, with δ13C values up to -4.1‰). If the Qaidam Basin was as arid as today in the Mio-Pliocene, these data would indicate that the majority of the animals had C3 diets and only a few individuals (besides the exceptional rhino CD0722) may have consumed some C4 plants. Based on geological evidence, however, the Qaidam Basin was probably warmer and more humid during the late Miocene and early Pliocene than today. Thus, these δ13C values likely indicate that many individuals had significant dietary intakes of C4 plants, and the Qaidam Basin had more C4 plants in the late Miocene and early Pliocene than today. Moreover, the Qaidam Basin likely had much denser vegetation at those times in order to support such large mammals as rhinos and elephants. While the δ18O values did not increase monotonously with time, the range of variation seems to have increased considerably since the early Pliocene, indicating increased aridification in the basin. The mean δ18O values of large mammals and those reconstructed for local meteoric waters display a significant negative shift in the late Miocene, consistent with the marine δ18O record which shows a cooling trend in the same period. Taken together, the isotope data suggest a warmer, wetter, and perhaps lower Qaidam Basin during the late Miocene and early Pliocene. Increased aridification after the early Pliocene is likely due to a combined effect of regional tectonism, which

  1. 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.

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

    Science.gov (United States)

    Wang, Kun; Jacobsen, Stein B.

    2016-10-01

    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.

  3. Culture Studies of Nitrogen and Oxygen Isotope Effects Associated with Nitrate Assimilation and Denitrification

    Science.gov (United States)

    Sigman, D. M.; Granger, J.; Lehmann, M. F.; Difiore, P. J.; Tortell, P. D.

    2007-12-01

    The isotope effects of nitrate-consuming reactions such as nitrate assimilation and denitrification are potential indicators of the physiological state of the organisms carrying out these reactions. Moreover, an understanding of these isotope effects is needed to use the stable isotopes to investigate the fluxes associated with these reactions in modern and ancient environments. We have used batch cultures to investigate the nitrogen (N) and oxygen (O) isotope effects of (1) nitrate assimilation by eukaryotic and prokaryotic algae and by heterotrophic bacteria, and (2) nitrate reduction by denitrifying bacteria. We observe intra- and inter-specific variation in isotope effect amplitudes and, in the case of denitrifiers, indications of isotope effect decreases during individual nitrate drawdown experiments. However, the measured N and O isotope effect ratio is close to 1 for all studied organisms, with the exception of an unusual denitrifier (Rhodobacter sphaeroides) that possesses only periplasmic (non-respiratory) nitrate reductase. This observation and other findings are consistent with nitrate reductase being the predominant source of isotope fractionation and with most isotope effect amplitude variability arising from variable degrees to which nitrate imported into the cell is reduced versus effluxed back into the environment; the more efflux, the more complete the expression of the fractionation imparted by nitrate reduction. If this is the case, then isotope effect amplitudes in the field should be related to physiological conditions in the environment, a prediction that, we argue, is supported by recent studies of (1) nitrate assimilation in the polar ocean and (2) denitrification in sediment porewaters.

  4. Brillouin scattering studies of isotopic effects in solid ammonia

    Science.gov (United States)

    Kiefte, H.; Penney, R.; Breckon, S. W.; Clouter, M. J.

    1987-01-01

    The technique of high resolution Brillouin spectroscopy has been used to determine the adiabatic elastic constants and the elasto-optic coupling (Pockels) coefficient ratios of oriented single crystals of (solid I) ND3 at temperatures near the gas-liquid-solid triple point. The values of the elastic constants at 196.0 K are C11=83.3, C12=44.0, and C44=49.6 (in units of kbar) with an estimated absolute uncertainty of ±2%. The values of the elasto-optic coefficient ratios are P12/P11=0.90 and P44/P11=0.16 for ND3 and 0.89 and 0.16 for NH3, respectively. Other than that expected from the mass ratio, no significant isotopic differences are evident.

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

    OpenAIRE

    2016-01-01

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD), than in H-tunneling. In order to examine the isoto...

  6. Trophic ecology of small yellow croaker (Larimichthys polyactis Bleeker): stable carbon and nitrogen isotope evidence

    Institute of Scientific and Technical Information of China (English)

    JI Weiwei; CHEN Xuezhong; JIANG Yazhou; LI Shengfa

    2011-01-01

    The trophic ecology of the small yellow croaker (Larimichthys polyactis) was studied using stable isotope analyses.Samples were collected from July to September 2009 and 34 individuals from eight sites were examined for stable carbon and nitrogen isotopes.Stable carbon isotope ratios (δ13C)ranged from -20.67 to -15.43,while stable nitrogen isotope ratios (δ15N) ranged 9.18-12.23.The relationship between δ13C and δ15N suggested high resource partitioning in the sampling area.Significant differences in stable isotope values among the eight sampling sites may be linked to environmental diversities involving various physical processes (such as ocean current,wind and tide) and different carbon sources.Furthermore,the stable isotope ratios may also explain the ontogenetic variability in diet and feeding,because δ13C and δ15N varied significantly with increasing body size.The findings are consistent with other studies on diet analyses in small yellow croaker.It was also demonstrated that stable isotope analysis could be used to estimate the trophic characters of small yellow croaker in feeding patterns and migrating habits.

  7. 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.

  8. Effects of short range correlations on Ca isotopes

    CERN Document Server

    Lalazissis, G A

    1996-01-01

    The effect of Short Range Correlations (SRC) on Ca isotopes is studied using a simple phenomenological model. Theoretical expressions for the charge (proton) form factors, densities and moments of Ca nuclei are derived. The role of SRC in reproducing the empirical data for the charge density differences is examined. Their influence on the depletion of the nuclear Fermi surface is studied and the fractional occupation probabilities of the shell model orbits of Ca nuclei are calculated. The variation of SRC as function of the mass number is also discussed.

  9. Isotope effect in charge-transfer collisions of H with He{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Loreau, J.; Dalgarno, A. [Institute for Theoretical Atomic, Molecular and Optical Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, Massachusetts 02138 (United States); Ryabchenko, S. [Northern (Arctic) Federal University, 17 Severnaya Dvina Emb., 163002 Arkhangelsk (Russian Federation); Laboratoire de Chimie Quantique et Photophysique, Universite Libre de Bruxelles (ULB), CP160/09, 1050 Bruxelles (Belgium); Vaeck, N. [Laboratoire de Chimie Quantique et Photophysique, Universite Libre de Bruxelles (ULB), CP160/09, 1050 Bruxelles (Belgium)

    2011-11-15

    We present a theoretical study of the isotope effect arising from the replacement of H by T in the charge-transfer collision H(n=2) + He{sup +}(1s) at low energy. Using a quasimolecular approach and a time-dependent wave-packet method, we compute the cross sections for the reaction including the effects of the nonadiabatic radial and rotational couplings. For H(2s) + He{sup +}(1s) collisions, we find a strong isotope effect at energies below 1 eV/amu for both singlet and triplet states. We find a much smaller isotopic dependence of the cross section for H(2p) + He{sup +}(1s) collisions in triplet states, and no isotope effect in singlet states. We explain the isotope effect on the basis of the potential energy curves and the nonadiabatic couplings, and we evaluate the importance of the isotope effect on the charge-transfer rate coefficients.

  10. Iron isotopes in ancient and modern komatiites: Evidence in support of an oxidised mantle from Archean to present

    Science.gov (United States)

    Hibbert, K. E. J.; Williams, H. M.; Kerr, A. C.; Puchtel, I. S.

    2012-03-01

    The mantle of the modern Earth is relatively oxidised compared to the initially reducing conditions inferred for core formation. The timing of the oxidation of the mantle is not conclusively resolved but has important implications for the timing of the development of the hydrosphere and atmosphere. In order to examine the timing of this oxidation event, we present iron isotope data from three exceptionally well preserved komatiite localities, Belingwe (2.7 Ga), Vetreny (2.4 Ga) and Gorgona (0.089 Ga). Measurements of Fe isotope compositions of whole-rock samples are complemented by the analysis of olivine, spinel and pyroxene separates. Bulk-rock and olivine Fe isotope compositions (δ57Fe) define clear linear correlations with indicators of magmatic differentiation (Mg#, Cr#). The mean Fe isotope compositions of the 2.7-2.4 Ga and 0.089 Ga samples are statistically distinct and this difference can be explained by greater extent of partial melting represented by the older samples and higher mantle ambient temperatures in the Archean and early Proterozoic relative to the present day. Significantly, samples of all ages define continuous positive linear correlations between bulk rock δ57Fe and V/Sc and δ57Fe and V, and between V/Sc and V with TiO2, providing evidence for the incompatible behaviour of V (relative to Sc) and of isotopically heavy Fe. Partial melting models calculated using partition coefficients for V at oxygen fugacities (fO2s) of 0 and + 1 relative to the fayalite-magnetite-quartz buffer (FMQ) best match the data arrays, which are defined by all samples, from late Archean to Tertiary. These data, therefore, provide evidence for komatiite generation under moderately oxidising conditions since the late Archean, and argue against a change in mantle fO2 concomitant with atmospheric oxygenation at ~ 2.4 Ga.

  11. The oxygen isotope effect on critical temperature in superconducting copper oxides

    OpenAIRE

    Mourachkine, A.

    2003-01-01

    The isotope effect provided a crucial key to the development of the BCS (Bardeen-Cooper-Schrieffer) microscopic theory of superconductivity for conventional superconductors. In superconducting cooper oxides (cuprates) showing an unconventional type of superconductivity, the oxygen isotope effect is very peculiar: the exponential coefficient strongly depends on doping level. No consensus has been reached so far on the origin of the isotope effect in the cuprates. Here we show that the oxygen i...

  12. Environmental effects on the stable carbon and oxygen isotopic ...

    African Journals Online (AJOL)

    USER

    2010-08-16

    Aug 16, 2010 ... Key words: Oxygen isotopes, carbon isotopes, Porites coral, density bands, skeletal .... isotopic ratio of CO2 gas derived from the Pee Dee Belemnite (PDB) ... water samples, a 2.0 ml of the sample was taken into a syringe and.

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

    Science.gov (United States)

    Van Kooten, Elishevah M. M. E.; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Olsen, Mia B.; Nordlund, Åke; Krot, Alexander N.; Bizzarro, Martin

    2016-01-01

    The short-lived 26Al radionuclide is thought to have been admixed into the initially 26Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent 54Cr and 26Mg*, the decay product of 26Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling 26Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived 26Al 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 26Mg*-depleted and 54Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived 26Al. The 26Mg* and 54Cr compositions of bulk metal-rich chondrites require significant amounts (25–50%) 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 that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants. PMID:26858438

  14. Atmospheric oxygen levels in the precambrian: a review of isotopic and geological evidence

    Science.gov (United States)

    Lambert, I. B.; Donnelly, T. H.

    1991-12-01

    The significant change in the sulfur isotope record in the early Proterozoic implies global scale oxidation of the previously reduced and sulfate-poor hydrosphere. Changes in the nature/abundance of uranium, iron and manganese deposits are consistent with the evolution of significant oxygen levels in the atmosphere in this period. It is suggested that global oxidation occurred in the early Proterozoic as a result of widespread development of sedimentary environments favourable for the proliferation of phytosynthetic organisms, coupled with steadily decreasing availability of ferrous iron, an important oxygen buffer, because of generally declining igneous and hydrothermal activity. There is a predominance of positive δ34S values for sulfides in Proterozoic carbonaceous strata and sediment-hosted mineral deposits, although the uncommonly preserved evaporitic sulfate deposits do not provide evidence of unusual 34S-enrichment in contemporaneous seawater. These data can be explained in terms of a supercontinent on which there was extensive sedimentation in major intracratonic troughs and platforms. This model is consistent with geological and palaeomagnetic data for this era. In the many sedimentary basins which had only occasional, or no, access to the open ocean, variably 34S-enriched sulfides accumulated by high rates and high degrees of biological sulfate reduction, and also by hydrothermal processes. Pyrite in Proterozoic open marine strata should have had mainly variable negative δ34S values, but few examples of such sequences occur in the geological record for this era. Late Proterozoic carbonates (ca. 900-600 m.y.) from different regions are characterised by mainly positive δ13C values. These are explained as the result of long-term global oceanic anoxia, which may have been a function of prolonged crustal stability preceding continental dispersion around the Proterozoic-Cambrian boundary. Significant rises in atmospheric oxygen levels would have resulted

  15. Molybdenum Evidence for Inherited Planetary Scale Isotope Heterogeneity of the Protosolar Nebula

    CERN Document Server

    Dauphas, N; Reisberg, L

    2001-01-01

    Isotope anomalies provide important information about early solar system evolution. Here we report molybdenum isotope abundances determined in samples of various meteorite classes. There is no fractionation of molybdenum isotopes in our sample set within 0.1 permil and no contribution from the extinct radionuclide 97Tc at mass 97 (97Tc/92Mo<3E-6). Instead, we observe clear anomalies in bulk iron meteorites, mesosiderites, pallasites, and chondrites characterized by a coupled excess in p- and r- or a mirror deficit in s-process nuclides (Mo-HL). This large scale isotope heterogeneity of the solar system observed for molybdenum must have been inherited from the interstellar environment where the sun was born, illustrating the concept of ``cosmic chemical memory''. The presence of molybdenum anomalies is used to discuss the filiation between planetesimals.

  16. Lead Contamination in Cocoa and Cocoa Products: Isotopic Evidence of Global Contamination

    National Research Council Canada - National Science Library

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

    2005-01-01

    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...

  17. Isotopic Evidence of Nitrate Sources and its Relationship to Algae in the San Joaquin River, California

    Science.gov (United States)

    Silva, S. R.; Kendall, C.; Young, M. B.; Stringfellow, W. T.; Borglin, S. E.; Kratzer, C. R.; Dahlgren, R. A.; Schmidt, C.; Rollog, M. E.

    2007-12-01

    Many competing demands have been placed on the San Joaquin River including deep water shipping, use as agricultural and drinking water, transport of agricultural and urban runoff, and recreation. These long-established demands limit the management options and increase the importance of understanding the river dynamics. The relationships among sources of water, nitrate, and algae in the San Joaquin River must be understood before management decisions can be made to optimize aquatic health. Isotopic analyses of water samples collected along the San Joaquin River in 2005-2007 have proven useful in assessing these relationships: sources of nitrate, the productivity of the San Joaquin River, and the relationship between nitrate and algae in the river. The San Joaquin River receives water locally from wetlands and agricultural return flow, and from three relatively large tributaries whose headwaters are in the Sierra Nevada. The lowest nitrate concentrations occur during periods of high flow when the proportion of water from the Sierra Nevada is relatively large, reflecting the effect of dilution from the big tributaries and indicating that a large fraction of the nitrate is of local origin. Nitrogen isotopes of nitrate in the San Joaquin River are relatively high (averaging about 12 per mil), suggesting a significant source from animal waste or sewage and/or the effects of denitrification. The d15N of nitrate varies inversely with concentration, indicating that these high isotopic values are also a local product. The d15N values of nitrate from most of the local tributaries is lower than that in the San Joaquin suggesting that nitrate from these tributaries does not account for a significant fraction of nitrate in the river. The source of the non-tributary nitrate must be either small unmeasured surface inputs or groundwater. To investigate whether groundwater might be a significant source of nitrate to the San Joaquin River, groundwater samples are being collected

  18. Isotope effect studies of the pyridoxal 5'-phosphate dependent histidine decarboxylase from Morganella morganii

    Energy Technology Data Exchange (ETDEWEB)

    Abell, L.M.; O' Leary, M.H.

    1988-08-09

    The pyridoxal 5'-phosphate dependent histidine decarboxylase from Morganella morganii shows a nitrogen isotope effect k/sup 14//k/sup 15/ = 0.9770 +/- 0.0021, a carbon isotope effect k/sup 12//k/sup 13/ = 1.0308 +/- 0.0006, and a carbon isotope effect for L-(..cap alpha..-/sup 2/H)histidine of 1.0333 +/- 0.0001 at pH 6.3, 37/sup 0/C. These results indicate that the overall decarboxylation rate is limited jointly by the rate of Schiff base interchange and by the rate of decarboxylation. Although the observed isotope effects are quite different from those for the analogous glutamate decarboxylase from Escherichia coli, the intrinsic isotope effects for the two enzymes are essentially the same. The difference in observed isotope effects occurs because of a roughly twofold difference in the partitioning of the pyridoxal 5'-phosphate-substrate Schiff base between decarboxylation and Schiff base interchange. The observed nitrogen isotope effect requires that the imine nitrogen in this Schiff base is protonated. Comparison of carbon isotope effects for deuteriated and undeuteriated substrates reveals that the deuterium isotope effect on the decarboxylation step is about 1.20; thus, in the transition state for the decarboxylation step, the carbon-carbon bond is about two-thirds broken.

  19. Submarine Hydrothermal Activity on the Aeolian Arc: New evidence from Helium Isotopes

    OpenAIRE

    Lupton, John; De Ronde, Cornel; Beker, Edward; Italiano, Francesco; Sprovieri, Mario; Bruno, Pier Paolo; FAURE, Kevin; Walker, Sharon

    2008-01-01

    In November 2007 we conducted a water-column and seafloor mapping study of the submarine volcanoes of the Aeolian Arc in the southern Tyrrhenian Sea aboard the R/V Urania. A total of 26 CTD casts were completed, 13 vertical casts and 13 tows. In addition to in situ measurements of temperature, conductivity, pressure and suspended particles, we also collected discrete samples for helium isotopes, methane, and trace metals. The helium isotope ratio, which is known to be an unambiguous indica...

  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. Neodymium and strontium isotope evidence for crustal contamination of continental volcanics.

    Science.gov (United States)

    Carter, S R; Evensen, N M; Hamilton, P J; O'nions, R K

    1978-11-17

    Combined neodymium and strontium isotope studies on Tertiary volcanics from northwest Scotland indicate that their parental mantle isotopic compositions have been substantially modified in many instances by contamination with the Precambrian continental crust through which they were erupted. The occurrence of samarium-neodymium and rubidium-strontium "pseudoisochrons" of different ages in these contaminated continental volcanics indicates that they are artifacts of the contamination processes and have no temporal significance with respect to mantle fractionation events.

  2. Chondritic osmium isotopic composition of late Archean convecting upper mantle:Evidence from Zunhua podiform chromitites, Hebei, North China

    Institute of Scientific and Technical Information of China (English)

    XIA Qiongxia; ZHI Xiachen; LI Jianghai; HUANG Xiongnan

    2004-01-01

    Podiform chromite deposits are a characteristic feature of the mantle sequences of harzburgitic ophiolites. The chromites usually have very low Re and high Os contents, which makes it the most resistant phase remaining from the primary magmatic history of the ultramafic sections of ophiolites. The podiform chromite is one of the robust indicators of initial Os isotopic compositions of the ophiolites where podiform chromites were derived from, which provides strong evidence for the origin and evolution of oceanic lithosphere. The Re and Os contents and the Os isotopic compositions of seven podiform chromitites from Zunhua ophiolitic mélange belt, North China are reported in this study. The Re contents range from 0.019 to 0.128 ng/g, Os from 8.828 to 354.0 ng/g, and the 187Os/188Os ratio from 0.11003 to 0.11145. Three massive chromitites among the sample set have very high Os contents (>300 ng/g), and their 187Os/188Os ratios range from 0.11021 to 0.11030, averaging 0.11026 ± 0.00005 (σ), equivalent to a γOs = -0.12 ± 0.06 at 2.6 Ga, which means that the Os isotopic composition of convecting upper mantle is chondritic in late Archean. It is the Os isotopic composition of podiform chromitites that are derived from the oldest ophiolite in the world till now.

  3. Isotopic evidence for trapped fissiogenic REE and nucleogenic Pu in apatite and Pb evolution at the Oklo natural reactor

    Science.gov (United States)

    Horie, Kenji; Hidaka, Hiroshi; Gauthier-Lafaye, François

    2004-01-01

    A part of the boundary layer of reactor zone 10 at the Oklo natural reactor shows a unique petrologic texture, which contains high-grade uraninite and massive apatite concretions. In order to study distribution behavior of fission products around the boundary between the reactor zone and the wall rock and to clarify the relation of migration mechanisms of fission products with geochemical factors, in-situ isotopic analyses of Nd, Sm, Gd, Pb and U in uraninite and apatite from the sample were performed by Sensitive High Resolution Ion Microprobe (SHRIMP). Sm and Gd isotopic ratios of uraninite and apatite show evidence of neutron irradiation with fluence between 4.4-6.8×10 19 n/cm 2. Judging from the isotopic anomalies of Nd and U, the apatite coexisting with the uraninite plays an important role in trapping fissiogenic LREE and nucleogenic 239Pu into the structure. Systematic Pb isotopic data from apatite, uraninite, galena and minium suggest the following chronological interpretations. The apatite formed 1.92±0.01 Ga ago and trapped fissiogenic light REE and nucleogenic 239Pu that migrated from the reactor during the criticality. The uraninite around the boundary between reactor and sandstone dissolved once 1.1˜1.2 Ga ago. Galena grains were formed by U-Pb mobilization in association with the intrusion of dolerite dyke 0.45˜0.83 Ga ago. Minium was derived from recent dissolution of galena under locally oxidizing conditions.

  4. Zinc isotope evidence for a large-scale carbonated mantle beneath eastern China

    Science.gov (United States)

    Liu, Sheng-Ao; Wang, Ze-Zhou; Li, Shu-Guang; Huang, Jian; Yang, Wei

    2016-06-01

    A large set of zinc (Zn) stable isotope data for continental basalts from eastern China were reported to investigate the application of Zn isotopes as a new tracer of deep carbonate cycling. All of the basalts with ages of 120 Ma basalts from eastern China (0.27 ± 0.06‰; 2sd). Given that Zn isotope fractionation during magmatic differentiation is limited (≤0.1‰), the elevated δ66Zn values reflect the involvement of isotopically heavy crustal materials (e.g., carbonates with an average δ66Zn of ∼0.91‰) in the mantle sources. SiO2 contents of the recycled Mg (Zn)-rich carbonates in the mantle beneath eastern China since the Late Mesozoic. Since Zn is a trace element in the mantle and Zn isotopic compositions of marine carbonates and the mantle differ markedly, we highlight Zn isotopes as a new and useful tool of tracing deep carbonate cycling in the Earth's mantle.

  5. Isotopic evidence for a link between agricultural irrigation and high arsenic concentrations in groundwater

    Science.gov (United States)

    Li, M.; Wang, Y.; Shock, E.

    2011-12-01

    An isotope-based survey was carried out in the Datong Basin, northern China to investigate the hydrogeology of groundwater with high arsenic concentrations. Oxygen isotope (δ18O), hydrogen isotope (δD) and radioactive hydrogen isotope (3H) measurements were conducted with the aim of characterizing the groundwater origins and flow dynamics in this arsenic-contaminated groundwater system. Groundwater dating results from 3H measurements show that groundwaters from 20m ~ 70m have a wide range of ages (10a~ 191a), indicating diverse groundwater sources. In contrast, deeper groundwaters (70m ~90m) display a narrower age range (35a ~ 47a). In addition, the shallow-aquifer (70m) possess relatively narrower isotopic ranges and mostly lighter isotopic ratios, from -12.8% to -8.88% and -97.6% to -71.7%, respectively. Comparison with the local meteoric water line shows that groundwater δ18O and δD values plot with a shallower slope, consistent with the arid-semiarid climate of the Datong Basin, as well as a meteoric origin of the groundwater, and points to precipitation as the dominant source of recharge to the deeper aquifers in the study area. Groundwaters with high arsenic concentrations (100μg/L ~ 309μg/L) mainly occur in aquifers at depths between 20m and 70m, while shallower (70m) groundwaters carry relatively lower arsenic concentrations (Science of the Total Environment 407(12): 3823-3835.

  6. Paleoclimatological change in the Late Neoproterozoic: Evidence from oxygen isotopes of phosphorite in Yangtze Platform, China

    Science.gov (United States)

    Ling, H.-F.; Jiang, S.-Y.; Feng, H.-Z.; Chen, J.-H.; Chen, Y.-Q.; Yang, J.-H.

    2003-04-01

    section. It is suggested that the phosphorite studied preserved primary oxygen isotopes, whereas d18Odolo values of the dolomite were altered by diagenesis. Potential causes for the overall increase trend of d18Ophos include increase in seawater d18O values and decrease in temperature. During the time span of about 10 ~ 30 Ma for the section deposition when no glaciation occurred, it seems not completely in reality to attribute the variation of more than 4‰ of d18O values to seawater change alone. To cause ~4.3‰ variation of d18Ophos, temperature would decrease about 15-20˚C, which is possible to happen in the Earth history (Lecuyer and Allemand, 2002). The following lines of evidence also support this view. The studied phosphorites were deposited after thaw of the Snowball Earth. During the Snowball Earth period, continental weathering was in minimum due to little precipitation. This, together with existence of volcanic CO2 emitting through the snowball, CO2 accumulated in the atmosphere up to very high level and thus the temperature would be very high soon after thaw of the Snowball Earth. This, combined with more precipitation, would cause progressive weathering. Enhanced weathering of continental rocks would draw down the CO2 of atmosphere and in turn cause cooling, which is consistent with temperature lowering of the period. Increase trend of Pb/Th ratio during the period is in good agreement with enhanced weathering. Pb and Th are both highly particle reactive elements in the ocean. However, their geochemical behaviors in weathering processes are potentially different. Pb is mainly contained in feldspar while Th is mainly hosted in accessory minerals such as monazite. During enhanced weathering processes feldspar can be altered and release Pb whereas monazite would usually survive. Therefore Pb/Th ratio in hydrogenic sediments would be an indicator of weathering intensity. Enhanced weathering would also provide more nutrition elements to ocean, resulting in

  7. A large solvent isotope effect on protein association thermodynamics.

    Science.gov (United States)

    Eginton, Christopher; Beckett, Dorothy

    2013-09-24

    Solvent reorganization can contribute significantly to the energetics of protein-protein interactions. However, our knowledge of the magnitude of the energetic contribution is limited, in part, by a dearth of quantitative experimental measurements. The biotin repressor forms a homodimer as a prerequisite to DNA binding to repress transcription initiation. At 20 °C, the dimerization reaction, which is thermodynamically coupled to binding of a small ligand, bio-5'-AMP, is characterized by a Gibbs free energy of -7 kcal/mol. This modest net dimerization free energy reflects underlying, very large opposing enthalpic and entropic driving forces of 41 ± 3 and -48 ± 3 kcal/mol, respectively. The thermodynamics have been interpreted as indicating coupling of solvent release to dimerization. In this work, this interpretation has been investigated by measuring the effect of replacing H2O with D2O on the dimerization thermodynamics. Sedimentation equilibrium measurements performed at 20 °C reveal a solvent isotope effect of -1.5 kcal/mol on the Gibbs free energy of dimerization. Analysis of the temperature dependence of the reaction in D2O indicates enthalpic and entropic contributions of 28 and -37 kcal/mol, respectively, considerably smaller than the values measured in H2O. These large solvent isotope perturbations to the thermodynamics are consistent with a significant contribution of solvent release to the dimerization reaction.

  8. Isotope effects on particle transport in the Compact Helical System

    Science.gov (United States)

    Tanaka, K.; Okamura, S.; Minami, T.; Ida, K.; Mikkelsen, D. R.; Osakabe, M.; Yoshimura, Y.; Isobe, M.; Morita, S.; Matsuoka, K.

    2016-05-01

    The hydrogen isotope effects of particle transport were studied in the hydrogen and deuterium dominant plasmas of the Compact Helical System (CHS). Longer decay time of electron density after the turning-off of the gas puffing was observed in the deuterium dominant plasma suggesting that the recycling was higher and/or the particle confinement was better in the deuterium dominant plasma. Density modulation experiments showed the quantitative difference of the particle transport coefficients. Density was scanned from 0.8  ×  1019 m-3 to 4  ×  1019 m-3 under the same magnetic field and almost the same heating power. In the low density regime (line averaged density  2.5  ×  1019 m-3) no clear difference was observed. This result indicates that the isotope effects of particle transport exist only in the low density regime. Comparison with neoclassical transport coefficients showed that the difference of particle transport is likely to be due to the difference of turbulence driven anomalous transport. Linear character of the ion scale turbulence was studied. The smaller linear growth rate qualitatively agreed with the reduced particle transport in the deuterium dominant plasma of the low density regime.

  9. Osmium isotope evidence for a crustal origin of platinum group elements in the Sudbury nickel ore, Ontario, Canada

    Science.gov (United States)

    Dickin, A. P.; Richardson, J. M.; Crocket, J. H.; McNutt, R. H.; Peredery, W. V.

    1992-09-01

    Sulphide ores from the International Nickel Company's (INCO) Creighton Mine, Sudbury, were analysed for osmium isotope ratios by ICP-MS. Rhenium and osmium abundances were determined by isotope dilution using a mixed spike in solid solution in a nickel sulphide matrix. Calculated initial 187Os /188Os ratios at 1.85 Ga (the emplacement age of the Sudbury complex) cluster around 0.60. The occurrence of less radiogenic compositions is attributed to post-emplacement, open-system behaviour of the Re/Os system. The Creighton results strongly overlap the initial ratios of published osmium data from two other Sudbury mines, suggesting a narrow range of isotope ratio in the original ore, within the range of estimated osmium isotope compositions in the country rock at 1.85 Ga, using published and new data. Therefore, the sulphide ores of the Sudbury complex can have an entirely crustal source without a mantle-derived contribution. This conclusion is consistent with published neodymium isotope data for the complex and supports the meteorite impact hypothesis, since this is the most effective means of fusing the large quantity of crustal rocks necessary to generate the complex. The extraction of platinum group elements (PGE) from this silicate melt by a nickel sulphide liquid was probably analogous to the laboratory fire assay procedure.

  10. Further evidence for three-nucleon spin-orbit interaction in isotope shifts of $Z=\\mathrm{magic}$ nuclei

    CERN Document Server

    Nakada, H

    2015-01-01

    We pointed out [Phys. Rev. C \\textbf{91}, 021302(R)] that the isotope shifts of the Pb nuclei, the kink at $N=126$ in particular, can be well described by the Hartree-Fock-Bogolyubov calculations if a density-dependent LS interaction derived from the $3N$ interaction is incorporated. Effects of the density-dependence in the LS channel on the isotope shifts are extensively investigated for the Ca, Ni and Sn isotopes, using the semi-realistic M3Y-P6 interaction and its LS modified variant M3Y-P6a, as in the Pb case. It is found that almost equal charge radii between $^{40}$Ca and $^{48}$Ca are reproduced, as well as the isotope shifts in a long chain of the Sn nuclei, owing to the density-dependence in the LS channel. A kink is predicted at $N=82$ for the isotope shifts of the Sn nuclei, in clear contrast to the interactions without the density-dependence.

  11. Temperature dependence of isotopic quantum effects in water.

    Science.gov (United States)

    Hart, R T; Benmore, C J; Neuefeind, J; Kohara, S; Tomberli, B; Egelstaff, P A

    2005-02-04

    The technique of high energy x-ray diffraction has been used to measure the temperature variation of hydrogen versus deuterium isotopic quantum effects on the structure of water. The magnitude of the effect is found to be inversely proportional to the temperature, varying by a factor of 2.5 over the range 6 to 45 degrees C. In addition, the H216O versus H218O effect has been measured at 26 degrees C and the structural difference shown to be restricted to the nearest neighbor molecular interactions. The results are compared to recent simulations and previously measured isochoric temperature differentials; additionally, implications for H/D substitution experiments are considered.

  12. Experimental evidence for hydrogen tunneling when the isotopic arrhenius prefactor (A(H)/A(D)) is unity.

    Science.gov (United States)

    Sharma, Sudhir C; Klinman, Judith P

    2008-12-31

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

  13. The physical chemistry of mass-independent isotope effects and their observation in nature.

    Science.gov (United States)

    Thiemens, Mark H; Chakraborty, Subrata; Dominguez, Gerardo

    2012-01-01

    Historically, the physical chemistry of isotope effects and precise measurements in samples from nature have provided information on processes that could not have been obtained otherwise. With the discovery of a mass-independent isotopic fractionation during the formation of ozone, a new physical chemical basis for isotope effects required development. Combined theoretical and experimental developments have broadened this understanding and extended the range of chemical systems where these unique effects occur. Simultaneously, the application of mass-independent isotopic measurements to an extensive range of both terrestrial and extraterrestrial systems has furthered the understanding of events such as solar system origin and evolution and planetary atmospheric chemistry, present and past.

  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. Sulfur and lead isotopic evidence of relic Archean sediments in the Pitcairn mantle plume

    Science.gov (United States)

    Delavault, Hélène; Chauvel, Catherine; Thomassot, Emilie; Devey, Colin W.; Dazas, Baptiste

    2016-11-01

    The isotopic diversity of oceanic island basalts (OIB) is usually attributed to the influence, in their sources, of ancient material recycled into the mantle, although the nature, age, and quantities of this material remain controversial. The unradiogenic Pb isotope signature of the enriched mantle I (EM I) source of basalts from, for example, Pitcairn or Walvis Ridge has been variously attributed to recycled pelagic sediments, lower continental crust, or recycled subcontinental lithosphere. Our study helps resolve this debate by showing that Pitcairn lavas contain sulfides whose sulfur isotopic compositions are affected by mass-independent fractionation (S-MIF down to Δ33S = -0.8), something which is thought to have occurred on Earth only before 2.45 Ga, constraining the youngest possible age of the EM I source component. With this independent age constraint and a Monte Carlo refinement modeling of lead isotopes, we place the likely Pitcairn source age at 2.5 Ga to 2.6 Ga. The Pb, Sr, Nd, and Hf isotopic mixing arrays show that the Archean EM I material was poor in trace elements, resembling Archean sediment. After subduction, this Archean sediment apparently remained stored in the deep Earth for billions of years before returning to the surface as Pitcairńs characteristic EM I signature. The presence of negative S-MIF in the deep mantle may also help resolve the problem of an apparent deficit of negative Δ33S anomalies so far found in surface reservoirs.

  16. 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.

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

    Science.gov (United States)

    Nelson, James A.; Rozar, Katherine L.; Adams, Charles S.; Wall, Kara R.; Switzer, Theodore S.; Winner, Brent L.; Hollander, David J.

    2015-01-01

    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. PMID:25834776

  18. Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ (13)C and δ (15)N).

    Science.gov (United States)

    Stallings, Christopher D; Nelson, James A; Rozar, Katherine L; Adams, Charles S; Wall, Kara R; Switzer, Theodore S; Winner, Brent L; Hollander, David J

    2015-01-01

    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.

  19. Early Eocene carbon isotope excursions: Evidence from the terrestrial coal seam in the Fushun Basin, Northeast China

    Science.gov (United States)

    Chen, Zuoling; Ding, Zhongli; Tang, Zihua; Wang, Xu; Yang, Shiling

    2014-05-01

    A series of transient global warming events between 56 and 50 Ma are characterized by a pronounced negative carbon isotope excursion (CIE). However, the documents of these hyperthermals, such as Eocene Thermal Maximum 2 and H2 events, have come chiefly from marine sediments, and their expression in terrestrial organic carbon is still poorly constrained. Here we yield a high-resolution carbon isotope record of terrestrial organic material from the Fushun Basin, which displays four prominent CIEs with magnitudes larger than 2.5‰. Based on age constraint and comparisons with deep-sea records, our data provide the first evidence of the four hyperthermals in coal seams and suggest a global significance of these events. Moreover, the difference of CIE magnitudes between marine and terrestrial records shows a significant linear correlation with the marine carbonate CIE, implying that these events are likely attributable to recurring injections of 13C-depleted carbon from submarine methane hydrates and/or permafrost.

  20. Stable Carbon Isotope Evidence for Neolithic and Bronze Age Crop Water Management in the Eastern Mediterranean and Southwest Asia.

    Science.gov (United States)

    Wallace, Michael P; Jones, Glynis; Charles, Michael; Fraser, Rebecca; Heaton, Tim H E; Bogaard, Amy

    2015-01-01

    In a large study on early crop water management, stable carbon isotope discrimination was determined for 275 charred grain samples from nine archaeological sites, dating primarily to the Neolithic and Bronze Age, from the Eastern Mediterranean and Western Asia. This has revealed that wheat (Triticum spp.) was regularly grown in wetter conditions than barley (Hordeum sp.), indicating systematic preferential treatment of wheat that may reflect a cultural preference for wheat over barley. Isotopic analysis of pulse crops (Lens culinaris, Pisum sativum and Vicia ervilia) indicates cultivation in highly varied water conditions at some sites, possibly as a result of opportunistic watering practices. The results have also provided evidence for local land-use and changing agricultural practices.

  1. 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.

  2. 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.

  3. 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.

  4. Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

    Science.gov (United States)

    Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

    2017-07-01

    In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon

  5. Sulfur isotope evidence for penetration of MVT fluids into igneous basement rocks, southeast Missouri, USA

    Science.gov (United States)

    Shelton, K. L.; Burstein, I. B.; Hagni, R. D.; Vierrether, C. B.; Grant, S. K.; Hennigh, Q. T.; Bradley, M. F.; Brandom, R. T.

    1995-08-01

    Previous studies of galena and sphalerite from Paleozoic MVT deposits in the Viburnum Trend, southeast Missouri documented large variations in δ34S values throughout the ore-forming event. The present study of Cu-Fe-sulfides reveals a similar δ34S variation that reflects two end-member sulfur reservoirs whose relative importance varied both temporally and spatially. More 34S-enriched sulfides (δ34S approaching 25‰) indicate introduction of sulfur from basinal sedimentary sources, whereas more 32S-enriched sulfides (δ34S Precambrian, igneous-hosted FeCu mineralization in southeast Missouri (West and Central Domes of Boss-Bixby) were investigated to elucidate their relationship to Cu-rich MVT orebodies hosted nearby within the overlying Cambrian Bonneterre Dolomite. Mineralization at Boss-Bixby is composed of an early phase of iron oxide deposition followed by Cu-Fe-sulfides. The Central Dome is faulted and its mineralization is more fracture-controlled than the typically podiform ores of the West Dome. The δ34S values of West Dome sulfides are 0.9 to 6.5‰ and pyrite-chalcopyrite indicate a temperature of 525° ± 50 °C. These data indicate an igneous source of sulfur during Precambrian ore deposition. In contrast, δ34S values of Central Dome sulfides are 9.4 to 20.0‰ and pyrite-chalcopyrite indicate temperatures of 275° ± 50 °C. Similar δ34S values are obtained for chalcopyrite from the overlying MVT deposits. We speculate that deeply circulating, basin-derived MVT fluids mobilized sulfur and copper from the underlying igneous basement and redeposited them in overlying Curich MVT orebodies, as well as overprinting earlier Precambrian sulfides of the Central Dome with a later, Paleozoic MVT sulfur isotope signature. Many models for MVT fluid circulation in the Midcontinent region of North America assume that igneous basement rocks are an impermeable boundary, but in southeast Missouri, evidence exists for structurally controlled MVT fluid movement

  6. Evolution of continental crust and mantle heterogeneity: Evidence from Hf isotopes

    Science.gov (United States)

    Jonathan, Patchett P.; Kouvo, O.; Hedge, C.E.; Tatsumoto, M.

    1982-01-01

    We present initial 176Hf/177 Hf ratios for many samples of continental crust 3.7-0.3 Gy old. Results are based chiefly on zircons (1% Hf) and whole rocks: zircons are shown to be reliable carriers of essentially the initial Hf itself when properly chosen on the basis of U-Pb studies. Pre-3.0 Gy gneisses were apparently derived from an unfractionated mantle, but both depleted and undepleted mantle are evident as magma sources from 2.9 Gy to present. This mantle was sampled mainly from major crustal growth episodes 2.8, 1.8 and 0.7 Gy ago, all of which show gross heterogeneity of 176Hf/177Hf in magma sources from ??Hf=0 to +14, or about 60% of the variability of the present mantle. The approximate ??Hf=2??Nd relationship in ancient and modern igneous rocks shows that 176Lu/177Hf fractionates in general twice as much as 147Sm/144Nd in mantle melting processes. This allows an estimation of the relative value of the unknown bulk solid/liquid distribution coefficient for Hf. DLu/DHf=??? 2.3 holds for most mantle source regions. For garnet to be an important residual mantle phase, it must hold Hf strongly in order to preserve Hf-Nd isotopic relationships. The ancient Hf initials are consistent with only a small proportion of recycled older cratons in new continental crust, and with quasi-continuous, episodic growth of the continental crust with time. However, recycling of crust less than 150 My old cannot realistically be detected using Hf initials. The mantle shows clearly the general positive ??Hf resulting from a residual geochemical state at least back to 2.9 Gy ago, and seems to have repeatedly possessed a similar degree of heterogeneity, rather than a continuously-developing depletion. This is consistent with a complex dynamic disequilibrium model for the creation, maintenance and destruction of heterogeneity in the mantle. ?? 1981 Springer-Verlag.

  7. Isotopic evidence of complex ground-water flow at Yucca mountain, Nevada, USA

    Science.gov (United States)

    Peterman, Zell E.; Stuckless, John S.

    1993-01-01

    Strontium isotopes (expressed as per mill deviation from mean sea water, ??87Sr) reflect interaction between ground water and the aquifer through which it is flowing. In the Cenozoic aquifer of the Yucca Mountain region, ??87Sr values increase from north to south downgradient in the flow system. The largest ??87Sr values occur in the Amargosa Desert where ground water probably encounters alluvial basin fill derived from Precambrian rocks in the Funeral Range. Similarly, large ??87Sr values for ground water in the Paleozoic aquifer at the western end of the Spring Mountains also probably reflect an encounter with Precambrian rocks. In several wells into the volcanic rocks, apparent isotopic disequilibrium between ground water and the producing units suggests that the ground water probably integrates over a substantial part of the saturated section in attaining its strontium isotope signature.

  8. Ruthenium endemic isotope effects in chondrites and differentiated meteorites

    Science.gov (United States)

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

    2010-07-01

    We report on the abundances of Ru isotopes in (1) iron meteorites, (2) stony-iron meteorites (pallasites), (3) ordinary and carbonaceous chondrites, and (4) in refractory inclusions from the carbonaceous meteorite Allende. We have developed improved Multiple-Collector, Negative-ion Thermal Ionization Mass Spectrometric (MC-NTIMS) techniques for Ru, with high ionization efficiency of 4% and with chemical separation techniques for Ru, which reduce mass interferences to the ppm level, so that no mass interference corrections needed to be applied. Our data were normalized to 99Ru/ 101Ru to correct for mass-dependent fractionation. We find no Ru isotopic effects in the ordinary chondrites and group IAB iron meteorites we have measured. There are significant effects (deficits) in the pure s-process nuclide 100Ru, in the Allende whole-rock and in refractory inclusions of up to 1.7 parts in 10,000 (ɛu). There are also endemic deficits in 100Ru in iron meteorites and in pallasites of up to 1.1 ɛu. The Ru data suggest a wide spread and large scale heterogeneity in p-, s-, and r-process components resulting in a deficit in s-process nuclides or enhancements in both p- and r-process nuclides, in refractory siderophiles condensing in the early solar nebula. In contrast, the data on bulk Murchison suggest an excess in 100Ru and in 104Ru, which are distinct from the rest of the measured patterns. Our results establish the presence of significant isotopic heterogeneity for Ru in the early solar nebula. The observation of endemic Ru effects in planetary differentiates, such as iron meteorites and pallasites, must reflect the siderophile nature of Ru and the preservation in condensing FeNi metal of refractory metal condensate grains formed in the early solar nebula. Once incorporated in the metal phase, the refractory siderophiles remained in the metal phase through the melting and differentiation of planetesimals to form FeNi cores and silicate mantles and crusts.

  9. Anomalous isotopic effect on electron-directed reactivity by a 3-{\\mu}m midinfrared pulse

    CERN Document Server

    Liu, Kunlong; Lan, Pengfei; Lu, Peixiang

    2012-01-01

    We have theoretically studied the effect of nuclear mass on electron localization in dissociating H_2^+ and its isotopes subjected to a few-cycle 3-{\\mu}m laser pulse. Compared to the isotopic trend in the near-infrared regime, our results reveal an inverse isotopic effect in which the degree of electron-directed reactivity is even higher for heavier isotopes. With the semi-classical analysis, we find, for the first time, the pronounced electron localization is established by the interferences through different channels of one- and, more importantly, higher-order photon coupling. Interestingly, due to the enhanced high-order above-threshold dissociation of heavier isotopes, the interference maxima gradually become in phase with growing mass and ultimately lead to the anomalous isotopic behavior of the electron localization. This indicates that the multi-photon coupling channels will play an important role in controlling the dissociation of larger molecules with midinfrared pulses.

  10. Detrital zircon evidence for Hf isotopic evolution of granitoid crust and continental growth

    Science.gov (United States)

    Iizuka, Tsuyoshi; Komiya, Tsuyoshi; Rino, Shuji; Maruyama, Shigenori; Hirata, Takafumi

    2010-04-01

    We have determined U-Pb ages, trace element abundances and Hf isotopic compositions of approximately 1000 detrital zircon grains from the Mississippi, Congo, Yangtze and Amazon Rivers. The U-Pb isotopic data reveal the lack of >3.3 Ga zircons in the river sands, and distinct peaks at 2.7-2.5, 2.2-1.9, 1.7-1.6, 1.2-1.0, 0.9-0.4, and uniformitarian secular change in Hf isotopes of granitoid crusts; Hf isotopic compositions of granitoid crusts deviate from the mantle evolution line from about 3.3 to 2.0 Ga, the deviation declines between 2.0 and 1.3 Ga and again increases afterwards. Consideration of mantle-crust mixing models for granitoid genesis suggests that the noted isotopic trends are best explained if the rate of crust generation globally increased in two stages at around (or before) 3.3 and 1.3 Ga, whereas crustal differentiation was important in the evolution of the continental crust at 2.3-2.2 Ga and after 0.6 Ga. Reconciling the isotopic secular change in granitoid crust with that in sedimentary rocks suggests that sedimentary recycling has essentially taken place in continental settings rather than active margin settings and that the sedimentary mass significantly grew through addition of first-cycle sediments from young igneous basements, until after ˜1.3 Ga when sedimentary recycling became the dominant feature of sedimentary evolution. These findings, coupled with the lack of zircons older than 3.3 Ga in river sands, imply the emergence of large-scale continents at about 3.3 Ga with further rapid growth at around 1.3 Ga. This resulted in the major growth of the sedimentary mass between 3.3 and 1.3 Ga and the predominance of its cannibalistic recycling later.

  11. Evidence for depletion of heavy silicon isotopes at comet 67P/Churyumov-Gerasimenko

    Science.gov (United States)

    Rubin, M.; Altwegg, K.; Balsiger, H.; Berthelier, J.-J.; Bieler, A.; Calmonte, U.; Combi, M.; De Keyser, J.; Engrand, C.; Fiethe, B.; Fuselier, S. A.; Gasc, S.; Gombosi, T. I.; Hansen, K. C.; Hässig, M.; Le Roy, L.; Mezger, K.; Tzou, C.-Y.; Wampfler, S. F.; Wurz, P.

    2017-05-01

    Context. The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) was designed to measure the composition of the gas in the coma of comet 67P/Churyumov-Gerasimenko, the target of the European Space Agency's Rosetta mission. In addition to the volatiles, ROSINA measured refractories sputtered off the comet by the interaction of solar wind protons with the surface of the comet. Aims: The origin of different solar system materials is still heavily debated. Isotopic ratios can be used to distinguish between different reservoirs and investigate processes occurring during the formation of the solar system. Methods: ROSINA consisted of two mass spectrometers and a pressure sensor. In the ROSINA Double Focusing Mass Spectrometer (DFMS), the neutral gas of cometary origin was ionized and then deflected in an electric and a magnetic field that separated the ions based on their mass-to-charge ratio. The DFMS had a high mass resolution, dynamic range, and sensitivity that allowed detection of rare species and the known major volatiles. Results: We measured the relative abundance of all three stable silicon isotopes with the ROSINA instrument on board the Rosetta spacecraft. Furthermore, we measured 13C/12C in C2H4, C2H5, and CO. The DFMS in situ measurements indicate that the average silicon isotopic composition shows depletion in the heavy isotopes 29Si and 30Si with respect to 28Si and solar abundances, while 13C to 12C is analytically indistinguishable from bulk planetary and meteorite compositions. Although the origin of the deficiency of the heavy silicon isotopes cannot be explained unambiguously, we discuss mechanisms that could have contributed to the measured depletion of the isotopes 29Si and 30Si.

  12. 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

  13. Oxygen isotopic evidence for vigorous mixing during the Moon-forming Giant Impact

    CERN Document Server

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

    2016-01-01

    Earth and Moon are shown here to be composed of oxygen isotope reservoirs that are indistinguishable, with a difference in {\\Delta}"17O of -1 +/- 5ppm (2se). Based on these data and our new planet formation simulations that include a realistic model for 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 {\\Delta}"17O within approximately 1 per mil of the terrestrial value, suggesting that these impactors were water rich.

  14. Origin of the Sudbury Complex by meteoritic impact: Neodymium isotopic evidence

    Science.gov (United States)

    Faggart, B.E.; Basu, A.R.; Tatsumoto, M.

    1985-01-01

    Samarium-neodymium isotopic data on whole rocks and minerals of the Sudbury Complex in Canada gave an igneous crystallization age of 1840 ?? 21 ?? 106 years. The initial epsilon neodymium values for 15 whole rocks are similar to those for average upper continental crust, falling on the crustal trend of neodymium isotopic evolution as defined by shales. The rare earth element concentration patterns of Sudbury rocks are also similar to upper crustal averages. These data suggest that the Sudbury Complex formed from melts generated in the upper crust and are consistent with a meteoritic impact.

  15. U and sr isotopes in ground water and calcite, yucca mountain, nevada: evidence against upwelling water.

    Science.gov (United States)

    Stuckless, J S; Peterman, Z E; Muhs, D R

    1991-10-25

    Hydrogenic calcite and opaline silica deposits in fault zones at Yucca Mountain, Nevada, have created considerable public and scientific controversy because of the possible development of a high-level nuclear waste repository at this location. Strontium and uranium isotopic compositions of hydrogenic materials were used to test whether the veins could have formed by upwelling of deep-seated waters. The vein deposits are isotopically distinct from ground water in the two aquifers that underlie Yucca Mountain, indicating that the calcite could not have precipitated from ground water. The data are consistent with a surficial origin for the hydrogenic deposits.

  16. 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...

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

    Science.gov (United States)

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

    2014-07-15

    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

  18. Isotope effect in tunnelling ionization of neutral hydrogen molecules

    CERN Document Server

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

    2015-01-01

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates (O.I. Tolstikhin, H.J. Worner and T. Morishita, Phys. Rev. A 87, 041401(R) (2013) [1]). We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H2/D2 gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H2 and D2. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  19. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules

    Science.gov (United States)

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

    2016-08-01

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

  20. Structural isotope effects in metal hydrides and deuterides.

    Science.gov (United States)

    Ting, Valeska P; Henry, Paul F; Kohlmann, Holger; Wilson, Chick C; Weller, Mark T

    2010-03-07

    Historically the extraction of high-quality crystallographic information from inorganic samples having high hydrogen contents, such as metal hydrides, has involved preparing deuterated samples prior to study using neutron powder diffraction. We demonstrate, through direct comparison of the crystal structure refinements of the binary hydrides SrH(2) and BaH(2) with their deuteride analogues at 2 K and as a function of temperature, that precise and accurate structural information can be obtained from rapid data collections from samples containing in excess of 60 at.% hydrogen using modern high-flux, medium resolution, continuous wavelength neutron powder diffraction instruments. Furthermore, observed isotope-effects in the extracted lattice parameters and atomic positions illustrate the importance of investigating compounds in their natural hydrogenous form whenever possible.

  1. Isotope quantum effects in water around the freezing point.

    Science.gov (United States)

    Hart, R T; Mei, Q; Benmore, C J; Neuefeind, J C; Turner, J F C; Dolgos, M; Tomberli, B; Egelstaff, P A

    2006-04-07

    We have measured the difference in electronic structure factors between liquid H(2)O and D(2)O at temperatures of 268 and 273 K with high energy x-ray diffraction. These are compared to our previously published data measured from 279 to 318 K. We find that the total structural isotope effect increases by a factor of 3.5 over the entire range, as the temperature is decreased. Structural isochoric temperature differential and isothermal density differential functions have been used to compare these data to a thermodynamic model based upon a simple offset in the state function. The model works well in describing the magnitude of the structural differences above approximately 310 K, but fails at lower temperatures. The experimental results are discussed in light of several quantum molecular dynamics simulations and are in good qualitative agreement with recent temperature dependent, rotationally quantized rigid molecule simulations.

  2. [The isotope effect in the glycine dehydrogenase reaction is the cause of the intramolecular isotope inhomogeneity of glucose carbon of starch synthesized during photorespiration].

    Science.gov (United States)

    Ivlev, A A

    2005-01-01

    The isotope distribution of glucose-6-phosphate in the main pathways of its biosynthesis (in the processes of CO2 assimilation and photorespiration in the Calvin cycle and during resynthesis from the degradation products of lipids and proteins) was analyzed. For reconstructing the isotope distribution of glucoso-6-phosphate synthesized in the Calvin cycle during photorespiration, the functioning of the cycle with regard to its coupling with the glycolate chain, which together constitute the photorespiration chain, was considered. In the glycine dehydrogenase reaction of the glycolate cycle, there arises an isotope effect, which determines the distribution of isotopes in the glucose-6-phosphate and other photorespiration products. The isotope effect of the glycine dehydrogenase reaction increases at the expense of the exhaustion of glucose resources feeding the photorespiration chain. As a result, atoms C-3 and C-4 of glucose become enriched with the heavy isotope, and subsequent mixing of atoms and the specificity of interactions in the photorespiration chain lead to an isotope weighting of the other atoms and an uneven distribution of carbon isotopes in glucose-6-phosphate and other photorespiration products. A comparison of the glucose-6-phosphate isotope patterns in different pathways of the synthesis with the experimental data on the distribution of carbon isotopes in starch glucose of storing plant organs led to the conclusion that the starch resources are predominantly formed at the expense of glucose-6-phosphate of photorespiration. This is consistent with the earlier observed enhancement of photorespiration at the stage of plant maturation.

  3. Ultrahigh-Temperature Metamorphism in Madurai Granulites, Southern India: Evidence from Carbon Isotope Thermometry.

    Science.gov (United States)

    Satish-Kumar

    2000-07-01

    Ultrahigh-temperature (UHT) metamorphism in the Madurai Block of the southern Indian granulite terrain has been verified using the calcite-graphite isotope exchange thermometer. Carbon isotope thermometry has been applied to marbles from a locality near the reported occurrence of sapphirine granulites that have yielded temperature estimates of around 1000 degrees C. The delta(13)C and delta(18)O values of calcite are homogenous, implying equilibration of the isotopes during metamorphism. However, the delta(13)C values of single graphite crystals show variations in the order of 1 per thousand within a hand specimen. Detailed isotopic zonation studies indicate that graphite preserves either the time-integrated crystal growth history or reequilibrium fractionation during its cooling history. The graphite cores preserve higher delta(13)C values than the rims. The fractionation between calcite and graphite cores gives the highest metamorphic temperature of about 1060 degrees C, which matches the petrologically inferred temperature estimates in the high-magnesian pelites. The fractionation between graphite rims and calcite suggests a temperature of around 750 degrees C, which is interpreted to reflect retrograde cooling. This event is also observed in the sapphirine granulites. Calcite-graphite thermometry thus provides a useful tool to define UHT metamorphism in granulite terrains.

  4. 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

    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...

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

    NARCIS (Netherlands)

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

    2016-01-01

    Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from t

  6. 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.

  7. 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.

  8. Observation of Selective Isotope Effect in the Ultraviolet excitation of N2: A Computational Study

    CERN Document Server

    Muskatel, B H; Thiemens, Mark H; Levine, R D

    2011-01-01

    Isotope effects associated with gas phase N2 photolysis are used to interpret Martian atmospheric evolution, icy satellite atmospheric chemistry and meteorite isotopic anomalies from nebular N2 photochemistry. To interpret observations at the highest level, fundamental understanding of the precise wavelength dependency of the process must be known. In this paper VUV isotopic photodissociation effects are calculated as a function of wavelength at different wavelength slices in the 12.5-15 eV range. A very strong wavelength dependence is observed, which is significant for experiments. An observable effect is possible for the width of the beam profile at the advanced light source, ALS that may produce sufficient photolysis product for high precision isotopic analysis. A significantly more pronounced effect is predicted for a beam narrower by a factor of four providing a potential experimental test of the model. The spectrum is computed ab initio. It manifests two physical mechanisms for the isotope effect and th...

  9. Nucleosynthetic molybdenum isotope anomalies in iron meteorites - new evidence for thermal processing of solar nebula material

    Science.gov (United States)

    Poole, Graeme M.; Rehkämper, Mark; Coles, Barry J.; Goldberg, Tatiana; Smith, Caroline L.

    2017-09-01

    We have investigated nucleosynthetic Mo isotope anomalies in 38 different bulk iron meteorites from 11 groups, to produce by far the largest and most precise dataset available to date for such samples. All magmatic iron groups were found to display deficits in s-process Mo isotopes, with essentially constant anomalies within but significant variations between groups. Only meteorites of the non-magmatic IAB/IIICD complex revealed terrestrial Mo isotopic compositions. The improved analytical precision achieved in this study enables two isotopically distinct suites of iron meteorites to be identified. Of these, the r=p suite encompasses the IC, IIAB, IIE, IIIAB, IIIE and IVA groups and exhibits relatively modest but 'pure' s-process deficits, relative to Earth. The second r>p suite includes groups IIC, IIIF and IVB. These iron meteorites show larger s-process deficits than the r=p suite, coupled with an excess of r-process relative to p-process components. Comparison of the results with data for other elements (e.g., Cr, Ni, Ru, Ti, Zr) suggests that the Mo isotope variability is most likely produced by thermal processing and selective destruction of unstable presolar phases. An updated model is proposed, which relates the iron meteorite suites to different extents of thermal processing in the solar nebula, as governed by heliocentric distance. In detail, the r=p suite of iron meteorite parent bodies is inferred to have formed closer to the Sun, where the extent of thermal processing was similar to that experienced by terrestrial material, so that the meteorites exhibit only small s-process deficits relative to Earth. In contrast, the r>p suite formed at greater heliocentric distance, where more subtle thermal processing removed a smaller proportion of r- and p-process host phases, thereby generating larger s-process deficits relative to the terrestrial composition. In addition, the thermal conditions enabled selective destruction of p- versus r-isotope carrier phases

  10. Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

    Science.gov (United States)

    Spooner, P.; Guo, W.; Robinson, L. F.

    2014-12-01

    Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

  11. Isotopic evidence for Last Glacial climatic impacts on Neanderthal gazelle hunting territories at Amud Cave, Israel.

    Science.gov (United States)

    Hartman, Gideon; Hovers, Erella; Hublin, Jean-Jacques; Richards, Michael

    2015-07-01

    The Middle Paleolithic site of Amud Cave, Israel, was occupied by Neanderthals at two different time periods, evidenced by two chronologically and stratigraphically distinct depositional sub-units (B4 and B2/B1) during MIS 4 and MIS 3, respectively. The composition of both hunted large fauna and naturally-deposited micromammalian taxa is stable at the site over time, despite a ∼ 10 ky gap between the two occupation phases. However, while gazelle is the most ubiquitous hunted species throughout the occupation, isotopic analysis showed that there is a marked change in Neanderthal hunting ranges between the early (B4) and late (B2/B1) phases. Hunting ranges were reconstructed by comparing oxygen, carbon, and strontium isotopes from gazelle tooth enamel with modern isotope data from the Amud Cave region. This region is characterized by extensive topographic, lithological, and pedological heterogeneity. During the early occupation phase negative oxygen isotope values, low radiogenic (87)Sr/(86)Sr ratios, and low Sr concentrations reveal restricted gazelle hunting in the high elevations west of Amud Cave. In the late occupation phase, hunting ranges became more diverse, but concentrate at low elevations closer to the site. Climatic proxies indicate that conditions were drier in the early occupation phase, which may have pushed gazelle populations into higher, more productive foraging areas. This study showed that Neanderthals adjusted their hunting territories considerably in relation to varying environmental conditions over the course of occupation in Amud Cave. It highlights the utility of multiple isotope analysis in enhancing the resolution of behavioral interpretations based on faunal remains and in reconstructing past hunting behaviors of Paleolithic hominins.

  12. Lake-groundwater relationships and fluid-rock interaction in the East African Rift Valley: isotopic evidence

    Science.gov (United States)

    Darling, W. George; Gizaw, Berhanu; Arusei, Musa K.

    1996-05-01

    The assessment of water resources in the Rift Valley environment is important for population, agriculture and energy-related issues and depends on a good understanding of the relationship between freshwater lakes and regional groundwater. This can be hampered by the amount of fluid-rock interaction which occurs throughout the rift, obscuring original hydrochemical signatures. However, O and H stable isotope ratios can be used as tracers of infiltration over sometimes considerable distances, while showing that the volcanic edifices of the rift floor have varying effects on groundwater flow patterns. Specific cases from Kenya and Ethiopia are considered, including Lakes Naivasha, Baringo, Awasa and Zwai. In addition to their physical tracing role, stable isotopes can reveal information about processes of fluid-rock interaction. The general lack of O isotope shifting in rift hydrothermal systems suggests a high water:rock ratio, with the implication that these systems are mature. Carbon isotope studies on the predominantly bicarbonate waters of the rift show how they evolve from dilute meteoric recharge to highly alkaline waters, via the widespread silicate hydrolysis promoted by the flux of mantle carbon dioxide which occurs in most parts of the rift. There appears to be only minor differences in the C cycle between Kenya and Ethiopia.

  13. Pyrite multiple-sulfur isotope evidence for rapid expansion and contraction of the early Paleoproterozoic seawater sulfate reservoir

    Science.gov (United States)

    Scott, Clint; Wing, Boswell A.; Bekker, Andrey; Planavsky, Noah J.; Medvedev, Pavel; Bates, Steven M.; Yun, Misuk; Lyons, Timothy W.

    2014-03-01

    Earth's oxygenation is often described in terms of two unidirectional steps at the beginning and end of the Proterozoic Eon, separated by a long-lived intermediate redox state. Recent work defines a more complicated path to oxygenation, exemplified by an apparent drop in oxidation state following the early Paleoproterozoic Lomagundi carbon isotope excursion. The timing of this proposed drop in oxidation state is not well constrained, and it is not clear how it relates to redox conditions during the remainder of the Proterozoic. Here we present a study of pyrite multiple-sulfur isotopes, supported by Fe speciation and organic carbon isotopes, from early Paleoproterozoic black shales. We find evidence for the rapid expansion of the seawater sulfate reservoir during the Great Oxidation Event at ca. 2.3 Ga followed by a subsequent contraction in the size of the seawater sulfate reservoir at ca. 2.05 Ga. This scenario is consistent with the emerging view of a rise and fall in surface oxidation state during the early Paleoproterozoic. Comparison of our new data to other records of the seawater sulfate reservoir suggests that the elevated sulfate concentrations that characterize the early Paleoproterozoic did not return until the late Neoproterozoic.

  14. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  15. 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

  16. 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.

  17. Silver diffusion and isotope effect in silver rubidium iodide

    Energy Technology Data Exchange (ETDEWEB)

    Arzigian, James Simon [Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Physics

    1980-01-01

    The diffusion coefficient of silver in (RbAg 4I 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-RbAg4I5 and beta-RbAg4I5, 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 K being 0.12 ± 0.01. The second-order phase transition at 208 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 involving ionic polarons, or cooperative motion, such as crowdions or solitons, seem consistent with the observed results.

  18. Tellurium isotopic composition of the early solar system—A search for effects resulting from stellar nucleosynthesis, 126Sn decay, and mass-independent fractionation

    Science.gov (United States)

    Fehr, Manuela A.; Rehkämper, Mark; Halliday, Alex N.; Wiechert, Uwe; Hattendorf, Bodo; Günther, Detlef; Ono, Shuhei; Eigenbrode, Jennifer L.; Rumble, Douglas

    2005-11-01

    New precise Te isotope data acquired by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS) are presented for selected extraterrestrial and terrestrial materials. Bulk samples of carbonaceous, ordinary and enstatite chondrites as well as the metal and sulfide phases of iron meteorites were analyzed to search for nucleosynthetic isotope anomalies and to find evidence of formerly live 126Sn, which decays to 126Te with a half-life of 234,500 yr. None of the meteorites show evidence of mass dependent Te isotope fractionations larger than 2‰ for δ 126/128Te. Following internal normalization of the data to 125Te/ 128Te, the Te isotope ratios of all analyzed meteorites were found to be identical to a terrestrial standard, within uncertainties. This provides evidence that the regions of the solar disk that were sampled during accretion of the meteorite parent bodies were well mixed and homogeneous on a large scale, with respect to Te isotopes. The data acquired for bulk carbonaceous chondrites indicate that the initial 126Sn/ 118Sn ratio of the solar system was <4 × 10 -5, but this is dependent on the assumption that no redistribution of Sn and Te occurred since the start of the solar system. Five Archean sedimentary sulfides that display both mass dependent and mass-independent isotope effects for S yield internally normalized Te isotope data, which indicate that mass-independent Te isotope effects are absent. The mass dependent fractionations in these samples are constrained to be less than ˜1‰ for δ 126/128Te.

  19. Evidence for the development of the Andean rain shadow from a Neogene isotopic record in the Atacama Desert, Chile

    Science.gov (United States)

    Rech, Jason A.; Currie, Brian S.; Shullenberger, Eric D.; Dunagan, Stan P.; Jordan, Teresa E.; Blanco, Nicolás; Tomlinson, Andrew J.; Rowe, Harry D.; Houston, John

    2010-04-01

    Varying ages from Triassic to Pliocene have been proposed for the onset of hyperaridity in the Atacama Desert. The exact timing for the initiation of hyperaridity is critical for determining potential causes, which range from regional effects of global cooling to Andean uplift above elevations conducive to extreme rain shadows. Analysis of the stable isotopic composition of lower Miocene-Quaternary (21-0.015 Ma) palustrine and lacustrine carbonates in the Calama Basin reveals extreme changes in their oxygen and carbon isotopic composition during the Miocene. Limestone δ18O values increased by ˜ 5‰ from middle to late Miocene, ranging from - 5.5‰ at 12 Ma to - 1‰ at ˜ 6 Ma. Carbon isotopic values increase by 9‰ over the Neogene, from average values of - 3‰ at 21 Ma to + 3‰ at 12 Ma, and reaching a maximum of + 6‰ at 5 Ma. The increase in oxygen isotopic values occurred over a time span in which the catchment area of the basin experienced significant uplift, causing the δ18O value of precipitation to become more negative. We attribute the shift towards higher δ18O values to enhanced evaporative enrichment both of soil water or snow prior to infiltration, and within shallow lakes or wetlands prior to carbonate precipitation. The large increase in δ13C values was likely caused by a transition from a vegetated landscape influenced primarily by soil-respired CO 2 to a landscape largely devoid of vegetation and influenced by atmospheric and volcanic CO 2. Isotopic values of palustrine carbonates therefore indicate that hyperaridity commenced in the Calama Basin during the middle to late Miocene, in agreement with other paleoclimatic records from the basin. The cause for the onset of this climate change is thought to be due to the development of a strong Andean rain shadow associated with the uplift of the Andes to mean elevations > 2 km.

  20. Isotopic Evidence for Massive Oxidation of Organic Matter Following the Great Oxidation Event

    Science.gov (United States)

    Kump, Lee R.; Junium, Christopher; Arthur, Michael A.; Brasier, Alex; Fallick, Anthony; Melezhik, Victor; Lepland, Aivo; CČrne, Alenka E.; Luo, Genming

    2011-12-01

    The stable isotope record of marine carbon indicates that the Proterozoic Eon began and ended with extreme fluctuations in the carbon cycle. In both the Paleoproterozoic [2500 to 1600 million years ago (Ma)] and Neoproterozoic (1000 to 542 Ma), extended intervals of anomalously high carbon isotope ratios (δ13C) indicate high rates of organic matter burial and release of oxygen to the atmosphere; in the Neoproterozoic, the high δ13C interval was punctuated by abrupt swings to low δ13C, indicating massive oxidation of organic matter. We report a Paleoproterozoic negative δ13C excursion that is similar in magnitude and apparent duration to the Neoproterozoic anomaly. This Shunga-Francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen-rich atmosphere.

  1. No K/T boundary at Anjar, Gujarat, India: Evidence from magnetic susceptibility and carbon isotopes

    Indian Academy of Sciences (India)

    H J Hansen; D M Mohabey; P Toft

    2001-06-01

    The paper describes the variation pattern of magnetic susceptibility of Lameta sediments and isotopic variation of organic 13C from Chui Hill, Bergi, Kholdoda, Pisdura and Girad. The susceptibility pattern and a negative carbon isotopic anomaly allows fixation of the K/T boundary at these localities and they dier in these aspects from the inter-trappean sediments at Anjar. Paleomagnetic measurements of the Anjar sediment and the overlying basalt ow demonstrate reversed polarity. The Lameta sediments with dinosaur nests at Kheda and the overlying intertrappean sediments are of normal polarity The clay layers at Anjar, associated closely with Ir-enrichments, are strongly leached, rhyolitic bentonites containing low-quartz paramorphs after high-quartz with glass inclusions. It is concluded, that the inter-trappean lake deposits at Anjar were deposited in the early part of magnetochron 29R and are unrelated to the K/T boundary.

  2. Isotopic evidences of groundwater circulation in the Kaidu River, South Tianshan Mountains, Central Asia

    Science.gov (United States)

    FAN, Yuting; Métivier, François; Chen, Yaning; He, Qing; Wang, Yun

    2015-04-01

    Water demand always exceeds supply in many parts of the world, especially in the arid and semi-arid regions. Groundwater is the primary input to hydrological systems like surface water bodies in polar and high mountain regions. A reasonable application of water isotopes requires a good understanding of the isotopic fractionation in processes controlling the isotopic composition of surface water and groundwater. Through the review of published papers, we find there is still scope for improving the understanding of groundwater isotopes: (1) quite few studies on groundwater circulation via kinetic fractionation of stable isotopes in the arid region of Central Asia; (2) several shortcomings on the quantitative assessment of water recycling for mountain-plain area. Tianshan Mountains, located in Xinjiang Province, is always called water tower in Central Asia and play an important role in the water cycle. In this paper, we implemented hydro-chemical index and Stable isotope mass balance method to study transformation of groundwater with surface water and to quantify recharge proportion between water bodies of typical regions. As a first step towards quantifying the contribution of groundwater, three-component mixing model of Kaidu River Basin into its constituent components has been done. Chemistry type of headstreams in this basin is mainly Ca-Mg-HCO3, while major ions and salinity of surface water show an increasing trend with the water rising time, which could be attributable to significant features of surface water evaporation and concentration. After that chemistry type of oasis-plain area in the basin is mainly Ca-HCO3-CO4. Groundwater recharge ratio was processed via spatial scale, it is only about 15% in upstream areas, while it accounted for 45% or more in the middle and lower reaches. Two groundwater recharge districts were divided according to the distribution characteristics of surface water. The first recharge district is from mountain area with spring

  3. 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.

  4. Multiple S-isotopic evidence for episodic shoaling of anoxic water during Late Permian mass extinction.

    Science.gov (United States)

    Shen, Yanan; Farquhar, James; Zhang, Hua; Masterson, Andrew; Zhang, Tonggang; Wing, Boswell A

    2011-02-22

    Global fossil data show that profound biodiversity loss preceded the final catastrophe that killed nearly 90% marine species on a global scale at the end of the Permian. Many hypotheses have been proposed to explain this extinction and yet still remain greatly debated. Here, we report analyses of all four sulphur isotopes ((32)S, (33)S, (34)S and (36)S) for pyrites in sedimentary rocks from the Meishan section in South China. We observe a sulphur isotope signal (negative δ(34)S with negative Δ(33)S) that may have resulted from limitation of sulphate supply, which may be linked to a near shutdown of bioturbation during shoaling of anoxic water. These results indicate that episodic shoaling of anoxic water may have contributed to the profound biodiversity crisis before the final catastrophe. Our data suggest a prolonged deterioration of oceanic environments during the Late Permian mass extinction.

  5. The nonmarine environment of Quaternary foraminifers in Yanshuzhuang, China: Evidence from boron and strontium isotopes

    Institute of Scientific and Technical Information of China (English)

    XIAO YingKai; XIAO Jun; ZHAO ZhiQi; HE MaoYong; LI ShiZhen

    2008-01-01

    The concentrations and isotopic compositions of boron and strontium of Quaternary foraminifers and bivalve fossils collected in the Yanghuzhuang section of Yanqing, Beijing and of modern gastropods living in the Guishui River and of river water were measured. The concentrations and isotopic compo-sitions of Quaternary foraminifers and bivalve fossils differed from those of modern marine fo-raminifers and were similar to those of modern terrestrial gastropods from the Guishui River. These results indicate that early Quaternary foraminifers in the Yanghuzhuang section inhabited a nonmarine environment and that these foraminifers were not the result of a transgression or sea flooding. The foraminifers were not special halobios and can survive in the terrestrial condition that resembled those of the ocean.

  6. 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

  7. Stable Isotopic Evidence for a Pedogenic Origin of Carbonates in Trench 14 near Yucca Mountain, Nevada.

    Science.gov (United States)

    Quade, J; Cerling, T E

    1990-12-14

    Layered carbonate and silica encrust fault fractures exposed in Trench 14 near Yucca Mountain, site of the proposed high-level nuclear waste repository in southern Nevada. Comparison of the stable carbon and oxygen isotopic compositions of the fracture carbonates with those of modern soil carbonates in the area shows that the fracture carbonates are pedogenic in origin and that they likely formed in the presence of vegetation and rainfall typical of a glacial climate. Their isotopic composition differs markedly from that of carbonate associated with nearby springs. The regional water table therefore remained below the level of Trench 14 during the time that the carbonates and silica precipitated, a period probably covering parts of at least the last 300,000 years.

  8. Chromium isotope evidence in ejecta deposits for the nature of Paleoproterozoic impactors

    Science.gov (United States)

    Mougel, Bérengère; Moynier, Frédéric; Göpel, Christa; Koeberl, Christian

    2017-02-01

    Non-mass dependent chromium isotopic signatures have been successfully used to determine the presence and identification of extra-terrestrial materials in terrestrial impact rocks. Paleoproterozoic spherule layers from Greenland (Grænsesø) and Russia (Zaonega), as well as some distal ejecta deposits (Lake Superior region) from the Sudbury impact (1849 ± 0.3 Ma) event, have been analyzed for their Cr isotope compositions. Our results suggest that 1) these distal ejecta deposits are all of impact origin, 2) the Grænsesø and Zaonega spherule layers contain a distinct carbonaceous chondrite component, and are possibly related to the same impact event, which could be Vredefort (2023 ± 4 Ma) or another not yet identified large impact event from that of similar age, and 3) the Sudbury ejecta record a complex meteoritic signature, which is different from the Grænsesø and Zaonega spherule layers, and could indicate the impact of a heterogeneous chondritic body.

  9. MAGNESIUM ISOTOPE EVIDENCE FOR SINGLE STAGE FORMATION OF CB CHONDRULES BY COLLIDING PLANETESIMALS

    Energy Technology Data Exchange (ETDEWEB)

    Olsen, Mia B.; Schiller, Martin; Krot, Alexander N.; Bizzarro, Martin [Centre for Star and Planet Formation, Natural History Museum of Denmark, University of Copenhagen, Copenhagen DK-1350 (Denmark)

    2013-10-10

    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 {sup 27}Al/{sup 24}Mg ratios of individual chondrules are positively correlated to their stable Mg-isotope composition (μ{sup 25}Mg), indicating that the correlated variability was imparted by a volatility-controlled process (evaporation/condensation). The mass-independent {sup 26}Mg composition (μ{sup 26}Mg*) of chondrules is consistent with single stage formation from an initially homogeneous magnesium reservoir if the observed μ{sup 25}Mg variability was generated by non-ideal Rayleigh-type evaporative fractionation characterized by a β value of 0.5142, in agreement with experimental work. The magnitude of the mass-dependent fractionation (∼300 ppm) is significantly lower than that suggested by the increase in {sup 27}Al/{sup 24}Mg values, indicating substantial suppression of isotopic fractionation during evaporative loss of Mg, possibly due to evaporation at high Mg partial pressure. Thus, the Mg-isotope data of skeletal chondrules from HH237 are consistent with their origin as melts produced in the impact-generated plume of colliding planetesimals. The inferred μ{sup 26}Mg* value of –3.87 ± 0.93 ppm for the CB parent body is significantly lower than the bulk solar system value of 4.5 ± 1.1 ppm inferred from CI chondrites, suggesting that CB chondrites accreted material comprising an early formed {sup 26}Al-free component.

  10. Isotopic Evidence for Microbial Activity in Crystalline Bedrock Fractures - a Case Study from Olkiluoto, SW Finland

    Science.gov (United States)

    Sahlstedt, E. K.; Karhu, J.; Pitkänen, P.

    2015-12-01

    Changes in the geochemical environment in crystalline bedrock fractures were investigated using the stable isotopes of C, O and S in fracture filling minerals as tracers. Of special interest were the possible changes which may occur in the subsurface at low temperatures. Especially, the influence of microbial activity was recognized as a catalyst for inducing changes in the geochemical environment. The study site is the Olkiluoto island located on the western coast of Finland, planned to host a geological repository for nuclear waste. Fracture surfaces were investigated to recognize the latest mineralizations at the site. These fillings were comprised of thin plates or small euhedral crystals of calcite and pyrite. The carbon and sulfur isotope compositions of calcite and pyrite were measured from bulk material by conventional IRMS, and in situ by secondary ion mass spectrometry. A notable feature of the late-stage fillings was high variabilities in the δ13C values of calcite and the δ34S values of pyrite, which ranged from -53.8 ‰ to +31.6 ‰ and from -50.4 ‰ to +77.7 ‰, respectively. Based on the isotopic compositions of the fillings, several features in the past hydrogeochemical environment could be recognized. The isotopic composition of the fracture fillings indicate an environment which was stratified with respect to depth. Characteristic features include bacterial sulfate reduction (BSR) occurring at depths 50 m. It appears that methanic conditions were replaced by sulfate reduction at depths >50 m likely due to infiltration of SO42--rich brackish waters. Sulfate reducing bacteria used mainly surface derived organic carbon as electron donors. Some indication of minor methanotrophic activity was recognized in anomalously low δ13C values of calcite, down to -53.8 ‰, at the depth range of 34-54 m. This methanotrophic activity may have been related to bacteria using CH4 as an electron donor in BSR.

  11. Isotopic evidence for quick freshening of magmatic chlorine in the Lesser Antilles arc volcanoes

    Science.gov (United States)

    Li, L.; Jendrzejewski, N.; Aubaud, C. P.; Bonifacie, M.; Crispi, O.; Dessert, C.; Agrinier, P.

    2012-12-01

    Despite numerous geophysical and geochemical monitoring techniques developed over the last 50 years to detect magma activities in volcanoes, it is still challenging to evaluate the state of magmatic activity during its decreasing phase (transitory quiet stage and/or final stage of the magma intrusion which may last for decades) for those infrequent, slow developing, and dangerous explosive eruptive arc volcanoes, attributed to the interaction between the magma and hydrothermal cells at shallow depths to produce complex phreato-magmatic events. Recent studies have implied that chloride in intrusion-induced thermal springs could be a potential sensitive indicator of shallow magma degassing. However, possible contamination from surface chlorine reservoirs, such as seawater, may overprint the magmatic signature and complicate the interpretation of field observation. Here, based on chlorine isotope examination of various water samples from two recently erupted volcanoes in the Lesser Antilles arc (Soufrière in Guadeloupe: phreatic eruption in1976-1977; Montagne Pelée in Martinique: pelean eruption in 1929-1932), we show that magmatic chlorine is isotopically distinct from surface chlorine (seawater, meteoric water, and ground water). A chlorine isotopic survey on thermal springs in Guadeloupe and Martinique indicate that the magmatic chlorine signature is still present in some of the thermal springs in Guadeloupe but completely disappeared in Martinique. This suggests that magmatic chlorine be rapidly flushed from hydrothermal system within < 30 to 80 years after the magmatic eruption. This enables chlorine isotopes to be a sensitive proxy to monitor shallow magmatic activities, particularly practicable at centennial scale.

  12. Cadmium-isotopic evidence for increasing primary productivity during the Late Permian anoxic event

    Science.gov (United States)

    Georgiev, Svetoslav V.; Horner, Tristan J.; Stein, Holly J.; Hannah, Judith L.; Bingen, Bernard; Rehkämper, Mark

    2015-01-01

    Earth's most extreme extinction event near the end of the Late Permian decimated more than 90% of all extant marine species. Widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe, though the driving mechanisms that sustained such conditions are still debated. Of particular interest is whether water column anoxia was a consequence of a 'stagnant ocean', or if it was controlled by increases in nutrient supply, primary productivity, and subsequent heterotrophic respiration. Testing these competing hypotheses requires deconvolving sedimentary/bottom water redox conditions from changes in surface water productivity in marine sediments. We address this issue by studying marine shales from East Greenland and the mid-Norwegian shelf and combining sedimentary redox proxies with cadmium-isotopic analyses. Sedimentary nitrogen-isotopic data, pyrite framboid analyses, and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling, and increasingly anoxic conditions with a strengthening upwelling in the Greenland and Norwegian sections, respectively. Detailed analysis of sedimentary metal budgets illustrates that Cd is primarily associated with organic carbon and records primary geochemical signatures, thus enabling reconstruction of surface water nutrient utilization. Cadmium-isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average δ114Cd110 of + 0.15 ± 0.01 ‰ (2 SE, n = 12; rel. NIST SRM 3108), indicative of incomplete surface water nutrient utilization up-section. The constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity - and not oceanic stagnation - to balance the larger nutrient fluxes to both study sites during the development of the Late Permian water column anoxia. Overall, our data illustrate that if bottom water redox and upwelling can be adequately constrained, Cd-isotopic analyses of

  13. Isotopic evidence for internal oxidation of the Earth's mantle during accretion

    Science.gov (United States)

    Williams, Helen M.; Wood, Bernard J.; Wade, Jon; Frost, Daniel J.; Tuff, James

    2012-03-01

    The Earth's mantle is currently oxidised and out of chemical equilibrium with the core. The reasons for this and for the relatively oxidised state of Earth's mantle relative to the mantles of other terrestrial planets are unclear. It has been proposed that the oxidised nature and high ferric iron (Fe3 +) content of Earth's mantle was produced internally by disproportionation of ferrous iron (Fe2 +) into Fe3 + and metallic iron by perovskite crystallisation during accretion. Here we show that there is substantial Fe isotope fractionation between experimentally equilibrated metal and Fe3 +-bearing perovskite (≥ 0.45‰/amu), which can account for the heavy Fe isotope compositions of terrestrial basalts relative to equivalent samples derived from Mars and Vesta as the latter bodies are too small to stabilise significant perovskite. Mass balance calculations indicate that all of the mantle's Fe3 + could readily have been generated from a single disproportionation event, consistent with dissolution of perovskite in the lower mantle during a process such as the Moon-forming giant impact. The similar Fe isotope compositions of primitive terrestrial and low-titanium lunar basalts is consistent with models of equilibration between the mantles of the Earth and Moon in the aftermath of the giant impact and suggests that the heavy Fe isotope composition of the Earth's mantle was established prior to, or during the giant impact. The oxidation state and ferric iron content of the Earth's mantle was therefore plausibly set by the end of accretion, and may be decoupled from later volatile additions and the rise of oxygen in the Earth's atmosphere at 2.45 Ga.

  14. Manganese oxide shuttling in pre-GOE oceans - evidence from molybdenum and iron isotopes

    Science.gov (United States)

    Kurzweil, Florian; Wille, Martin; Gantert, Niklas; Beukes, Nicolas J.; Schoenberg, Ronny

    2016-10-01

    The local occurrence of oxygen-rich shallow marine water environments has been suggested to significantly predate atmospheric oxygenation, which occurred during the Great Oxidation Event (GOE) ca. 2.4 billion years ago. However, the potential influence of such 'oxygen oases' on the mobility, distribution and isotopic composition of redox sensitive elements remains poorly understood. Here, we provide new molybdenum and iron isotopic data from shallow marine carbonate and silicate iron formations of the Koegas Subgroup, South Africa, that confirm local ocean redox stratification prior to the GOE. Mn concentrations correlate negatively with both δ98 Mo and δ56 Fe values, which highlights the substantial role of particulate manganese for the cycling of Mo and Fe in the Paleoproterozoic oceans. Based on these trends we propose that pore water molybdate was recharged (1) by the diffusional transport of seawater molybdate with high δ98 Mo and (2) by the re-liberation of adsorbed molybdate with low δ98 Mo during Mn oxide dissolution within the sediment. The relative contribution of isotopically light Mo is highest close to a Mn chemocline, where the flux of Mn oxides is largest, causing the negative correlation of Mn concentrations and δ98 Mo values in the Koegas sediments. The negative correlation between δ56 Fe values and Mn concentrations is likely related to Fe isotope fractionation during Fe(II) oxidation by Mn oxides, resulting in lower δ56 Fe values in the uppermost water column close to a Mn chemocline. We argue that the preservation of these signals within Paleoproterozoic sediments implies the existence of vertically extended chemoclines with a smoother gradient, probably as a result of low atmospheric oxygen concentrations. Furthermore, we suggest that abiotic oxidation of Fe(II) by a Mn oxide particle shuttle might have promoted the deposition of the Koegas iron formations.

  15. 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.

  16. Nd-isotope evidence for the distal provenance of the historical (c. Gabon (Western Africa)

    Science.gov (United States)

    Thiéblemont, D.; Guerrot, C.; Négrel, Ph.; Braucher, R.; Bourlès, D. L.; Thiéblemont, R.

    2014-12-01

    Surficial formations in Gabon, as well as in other places of western Central Africa include a ubiquitous, homogeneous and 1-3 m-thick clayey to sandy lateritic surface cover known as the 'Cover Horizon'. From 14C radiometric dating it has been concluded that the emplacement of this unit was correlative with a major environmental crisis which affected Central Africa c. 3000-2000 years ago. 10Be and Nd-isotopic analyses have been performed to provide new constraints on the age and origin of this layer. Six samples from two depth profiles investigated for 10Be exhibit an almost constant concentration consistent with a very recent deposition age. Nd-isotopic analyses performed on the silt to clay fraction of eleven samples from widely spaced locations over Gabon attest for mildly radiogenic signatures (εNd = -23 to -17) in ten of them, and a slightly radiogenic signature (εNd = -9) in one sample. TDM model ages range from 1.6 to 2.6 Ga, and a perfect discrimination is observed between the Nd-isotopic signature of the Cover Horizon and that of the underlying Congo Craton. This makes an aeolian origin as the most probable for the Cover Horizon. The average εNd (c. -20) is however rather unusual for aeolian sediments or aerosols. A possible source of particles is therefore tested by considering the present-day atmospheric flux over Gabon and adjacent regions. Combined atmospheric modeling and Nd-isotopes leads to the conclusion that the fine fraction of the Cover Horizon could have originated from the northern part of the Namib desert.

  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. Lead sources and transfer in the coastal Mediterranean: evidence from stable lead isotopes in marine particles

    Science.gov (United States)

    Alleman, L. Y.; Hamelin, B.; Véron, A. J.; Miquel, J.-C.; Heussner, S.

    Time series of settling and suspended particles have been collected by sediment traps and in situ pumps respectively, under contrasted hydrographic conditions in the Gulf of Lions and the Ligurian Sea, northwestern Mediterranean. Lead concentrations measured in sediment trap samples vary from 41±7 ppm in the Ligurian Sea to 58±10 ppm in the Gulf of Lions. These concentrations, 2-10 times lower than those measured previously in the Gulf of Lions, reflect the reduction of lead fallout from gasoline during the last decade. While atmospheric lead still originates mainly from anthropogenic emissions (automotive and industrial exhausts), stable lead isotopes demonstrate that anthropogenic and lithogenic lead are in similar proportions in the marine particles from the northwestern Mediterranean. Sequential extraction analyses performed on trap samples suggest that the isotopic variations can be explained by a three-component mixing between anthropogenic, natural soluble, and natural refractory sources. In the suspended particulate matter from the Gulf of Lions, lead concentrations range from 0.2 to 30 ng/ l, with isotopic compositions comparable to those of the settling particles ( 206Pb/ 207Pb from 1.165 to 1.178). This indicates a common origin in these two types of particles, probably mainly controlled by the Rhône River discharge and by resuspension processes on the continental shelf. By contrast, lead concentrations are lower in the suspended matter samples from the Ligurian Sea (0.5 to 1.7 ng/ l). In this case, the isotopic signature (1.165±0.002) is in equilibrium with the dissolved fraction, as previously found in other oligotrophic sites in the open ocean, where the suspended particles are mainly of biological origin and lead essentially authigenic in these particles.

  19. Fluid inclusion and isotopic evidence on dolomitization, Devonian of Western Canada

    Energy Technology Data Exchange (ETDEWEB)

    Aulstead, K.L.; Spencer, R.J.; Krouse, H.R. (Univ. of Calgary, Alberta (Canada))

    1988-05-01

    The Presqu'ile and Manetoe Facies are diagenetic features developed in Lower and Middle Devonian Formations of the Elk Point Basin (Presqu'ile) and the Mackenzie Shelf (Manetoe). Both facies contain coarsely crystalline dolomite and white sparry dolomite cement. Less extensive diagenetic phases, in order of paragenesis, include fluorite, anhydrite, barite, calcite, quartz, sphalerite and galena. Conditions of dolomitization are outlined from core and outcrop examination, thin section and cathodoluminescent petrography, fluid inclusion analyses, and C and O isotopic data. Fluid inclusion and stable isotope analyses from dolomite are combined to determine the isotopic composition of the dolomitizing fluids. Chemical analyses of fluid inclusion waters are compared with formation water analyses to derive a proposed origin for the diagenetic fluids. Dolomite formed from hot, high salinity fluids early in the diagenetic history of the basin. Limestone was dolomitized as a result of the same process that created white sparry dolomite cement in the Manetoe Facies. Remnants of the dolomitizing fluids are present as formation waters in some Devonian formations in Alberta. Subsequent invasion of meteoric waters produced more dilute diagenetic fluids which resulted in the precipitation of calcite and quartz cement in the Manetoe Facies. These fluids are present in fluid inclusions and are responsible for the low {sup 18}O content of the calcite cement. The temperatures of calcite and quartz formation differ as a function of burial depth within the Manetoe Facies during the Mesozoic and Cenozoic, while the temperature of formation for dolomite does not.

  20. Differential host use in two highly specialized ant-plant associations: evidence from stable isotopes.

    Science.gov (United States)

    Trimble, S T; Sagers, C L

    2004-01-01

    Carbon and nitrogen stable isotopes were used to examine variation in ant use of plant resources in the Cecropia obtusifolia / Azteca spp. association in Costa Rica. Tissue of ants, host plants and symbiotic pseudococcids were collected along three elevation transects on the Pacific slope of Costa Rica's Cordillera Central, and were analyzed for carbon and nitrogen isotopic composition. Worker carbon and nitrogen signatures were found to vary with elevation and ant colony size, and between Azteca species groups. Ants in the A. constructor species group appear to be opportunistic foragers at low elevations, but rely more heavily on their host plants at high elevations, whereas ants in the A. alfari species group consume a more consistent diet across their distribution. Further, isotope values indicate that both ant species groups acquire more nitrogen from higher trophic levels at low elevation and when ant colonies are small. Provisioning by the host is a substantial ecological cost to the interaction, and it may vary, even in a highly specialized association. Nonetheless, not all specialized interactions are equivalent; where interaction with one ant species group appears conditional upon the environment, the other is not. Differential host use within the Cecropia-Azteca association suggests that the ecological and evolutionary benefits and costs of association may vary among species pairs.

  1. Signatures of the source for the Emeishan flood basalts in the Ertan area: Pb isotope evidence

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The Emeishan flood basalts can be divided into high-Ti (HT) basalt (Ti/Y>500) and low-Ti (LT) basalt (Ti/Y<500). Sr, Nd isotopic characteristics of the lavas indicate that the LT- and the HT-type magmas originated from distinct mantle sources and parental magmas. The LT-type magma was derived from a shallower lithospheric mantle, whereas the HT-type magma was derived from a deeper mantle source that may be possibly a mantle plume. However, few studies on the Emeishan flood basalts involved their Pb isotopes, especially the Ertan basalts. In this paper, the authors investigated basalt samples from the Ertan area in terms of Pb isotopes, in order to constrain the source of the Emeishan flood basalts. The ratios of 206Pb/204Pb (18.31-18.41), 207Pb/204Pb (15.55-15.56) and 208Pb/204Pb (38.81-38.94) are significantly higher than those of the depleted mantle, just lying between EM I and EM II. This indicates that the Emeishan HT basalts (in the Ertan area) are the result of mixing of EMI end-member and EMII end-member.

  2. 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.

  3. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

    Science.gov (United States)

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

    2016-07-01

    The terminal Neoproterozoic Era (850-542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S~+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere.

  4. 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 cocoa and chocolate products were as high as 230 and 70 ng/g, respectively, which are consistent with market-basket surveys that have repeatedly listed lead concentrations in chocolate products among the highest reported for all foods. One source of 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.

  5. Isotope effect on gyro-fluid edge turbulence and zonal flows

    CERN Document Server

    Meyer, Ole Hauke Heinz

    2016-01-01

    The role of ion polarisation and finite Larmor radius on the isotope effect on turbulent tokamak edge transport and flows is investigated by means of local electromagnetic multi-species gyro-fluid computations. Transport is found to be reduced with the effective plasma mass for protium, deuterium and tritium mixtures. This isotope effect is found for both cold and warm ion models, but significant influence of finite Larmor radius and polarisation effects are identified. Sheared flow reduction of transport through self generated turbulent zonal flows and geodesic acoustic modes in the present model (not including neoclassical flows) is found to play only a minor role on regulating isotopically improved confinement.

  6. Mantle CO2 degassing through the Icelandic crust: Evidence from carbon isotopes in groundwater

    Science.gov (United States)

    Stefánsson, Andri; Sveinbjörnsdóttir, Árný E.; Heinemeier, Jan; Arnórsson, Stefán; Kjartansdóttir, Ríkey; Kristmannsdóttir, Hrefna

    2016-10-01

    Carbon isotopes of groundwater in Iceland were studied in order to determine the source and reactions of carbon at divergent plate boundaries not associated with active volcanic systems. All the waters were of meteoric origin, with temperatures of 1-130 °C, pH of ∼4.5-10.5 and dissolved inorganic carbon (∑CO2) between 1.8 and 4100 ppm. The measured range of δ13CO2 and 14CO2 in these waters was large, -27.4 to +2.0‰ and 0.6-118 pMC, respectively. The sources and reactions of dissolved inorganic carbon were studied by comparing the measured chemical and isotope composition with those simulated using isotope geochemical models. Three major sources of CO2 were identified: (1) dissolution of partially degassed basaltic rocks formed at the surface or shallow depths, (2) atmospheric CO2 through air-water exchange at surface, and (3) input of gas at depth into the groundwater systems that has similar carbon and isotope composition as the pre-erupted melt of the upper mantle and lower crust beneath Iceland. In the groundwater systems the CO2 chemistry and isotope content are modified due to carbonate mineral precipitation and changes in aqueous species distribution upon progressive water-rock interaction; these changes needed to be quantified in order to reveal the various CO2 sources. The CO2 flux of the Icelandic crust was estimated to be ∼5-10 · 1010 mol/yr with as high as 50% of the flux not associated with active volcanic centers but placed off-axis where a significant proportion of the CO2 may originate from the mantle. The mantle input of the groundwater off-axis corresponds to CO2 partial pressures of ∼10-6-1 bar and to a mantle CO2 flux of <5 · 105 mol/km2/yr for most areas and up to 125 · 105 and 1600 · 105 for the Southern Lowlands and Snæfellsnes Peninsula, respectively. The CO2 flux from active volcanic geothermal systems in Iceland was estimated to be ∼500-3000 · 105 mol CO2/km2/yr, considerably greater than the highest values observed off-axis.

  7. Re-Os and S isotope evidence for the origin of Platreef mineralization (Bushveld Complex)

    Science.gov (United States)

    Yudovskaya, M.; Belousova, E.; Kinnaird, J.; Dubinina, E.; Grobler, D. F.; Pearson, N.

    2017-10-01

    The Bushveld Complex contains the largest platinum-group element (PGE) deposits of the world that are represented by persistent stratiform reefs highly enriched with PGE with respect to underlying and overlying rocks. New Re-Os isotope and elemental LA MC-ICPMS data on platinum-group minerals (PGM) from the mineralized reefs are presented with implications to correlation between the different segments of the Bushveld Complex and a role of superimposed processes at the reef formation. We analyzed laurite (RuS2), hollingworthite (RhAsS), sperrylite (PtAs2) and Pt-Fe alloys from the Merensky Reef, Pseudoreef and the PGE reef of the Platreef. The measured 187Os/188Os value for Platreef laurite is 0.1751 ± 0.0004 whereas the ratios for sperrylite and hollingworthite range to slightly higher values (0.1713-0.1818 and 0.1744-0.1835 respectively). The observed textures of the analyzed PGM, such as Pt-Fe symplectites in base metal sulfides (BMS), laurite inclusions in chromite and sperrylite rims around sulfide-silicate aggregates, are interpreted as features of primary magmatic crystallization whereas hollingworthite overgrowths and exsolutions in sperrylite are likely to have originated from later solid state transformation or metasomatic processes. The Platreef is a composite sill-like body in the northern limb correlative to the Critical Zone in terms of stratigraphic position, whole-rock geochemistry and isotope characteristics. The pristine magmatic character of sulfides and PGM in the stratiform reefs at the top of the Platreef strongly resembles the style of Merensky Reef mineralization. However, the basal part of the Platreef pyroxenitic sequence is variably contaminated and mineralized with a significant hydrothermal overprint. Sulfides from underlying Lower Zone peridotite yield δ34S values varying from +9‰ to +14.2‰ that are much higher than the values for the overlying Platreef and are a consequence of sulfur assimilation from sedimentary sulfates. The

  8. 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...

  9. 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.

  10. Dynamic isotope effects on relaxation of quadrupolar nuclei in 12 simple organic molecules

    Institute of Scientific and Technical Information of China (English)

    毛希安; andM.Holz

    1995-01-01

    Dynamic isotope effects on relaxation rate of quadrupolar nuclei are preliminarily reported. The relaxation rates of 17O and 14N in 12 simple organic molecules and their 18 corresponding deuterated species have been systematically measured. The principal components of the molecular inertia tensors have been calculated. The results show that there is an intrinsic correlation between the dynamic isotope effects of the relaxation rate and the static isotope effects of the molecular inertia. The concepts of molecular collision frequency and translation-rotation coupling have been introduced into the NMR relaxation theory. Therefore, a reasonable explanation of the experimental results has been given.

  11. 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.

  12. Patterns of mortality among South Florida Manatees: Evidence from oxygen, sulfur and deuterium stable isotopes

    Science.gov (United States)

    MacAvoy, S. E.; Bacalan, V.; Kazantseva, M.; Rhodes, J.; Kim, K.

    2012-12-01

    The Florida manatee (Trichechus manatus latirostris) is an endangered marine mammal whose coastal habitat has been heavily altered by human development. Sources of mortality include anthropogenic and environmental causes. Necropsies were completed on 75 deceased individuals, and tissues, including bone samples, were collected for later analysis. This study investigates the utility of manatee bone stable oxygen (δ18O), sulfur (δ34S) and deuterium (δD) for determining where the animals lived (which may not be where they where their bodies were recovered), and the relative importance of marine versus freshwater for the individual animals. The isotopes can provide a "geochemical map" showing the distribution of mortality, aiding in the evaluation of geographical patterns in mortality. The δ18O signatures of the bones ranged from 14 to 18.5‰, with no significant difference between male and female mean values. δ18O significantly decreased with increasing latitude (p=.0016), a trend positively correlated with coastal Florida seawater δ18O literature values obtained from the NASA Global Seawater Oxygen-18 Database (http://data.giss.nasa.gov/o18data/) and the EAIA stable isotope database (http://www.univie.ac.at/cartography/project/wiser/). Bone δ34S indicated the influence of marine versus coastal freshwater dietary sources on the animals. Most individuals showed 34S-depleted signatures, which indicated a non-marine sulfur source; however some individuals clearly had taken up marine sulfate (mean 4.9 ± 3.7‰, range 0.8 to 13.8‰). Deuterium values were not available at the time this abstract was written, however we hypothesize that those values will co-vary with δ18O. We conclude that manatee diets are based on both marine and freshwater sources, but freshwater sources exert more influence. Marine water and manatee δ18O co-vary with latitude, suggesting that stable oxygen isotopes may be useful indicators of the latitude where manatees lived.

  13. Prolonged and recurrent global seafloor anoxia in the Early Triassic from uranium isotopic evidence

    Science.gov (United States)

    Lau, K. V.; Maher, K.; Kelley, B. M.; Yu, M.; Lehrmann, D. J.; Payne, J.

    2013-12-01

    The end-Permian extinction and prolonged Early Triassic recovery of marine ecosystems have been attributed in part to marine anoxia. However, the spatial and temporal extent of anoxic waters during Early Triassic time remains poorly understood. To better constrain the evolution of seawater conditions, we present a record of δ238/235U and uranium concentrations collected from the Great Bank of Guizhou, a Late Permian to Late Triassic isolated carbonate platform in the Nanpanjiang Basin, South China. The isotopic composition and concentration of uranium are independent constraints on paleoredox conditions and can be used as indicators for the global extent of ocean anoxia. Our δ238/235U results demonstrate that two large negative excursions of up to ~-0.4‰ occurred in the Induan and in the Spathian, before stabilizing in the Middle Triassic at Late Permian values. Uranium concentrations mirror the isotopic trends, reaching sustained minima of less than 0.2 ppm that correspond to the most negative isotopic values. By placing these observational constraints on a box model of the geological uranium cycle, we calculate that up to half of the continental shelves may have been affected during the two pulses of bottom-water anoxia. The expansion, contraction, and re-expansion of extreme low-oxygen conditions could explain many unresolved aspects of the prolonged recovery of marine ecosystems. The recurrence of widespread anoxia during Spathian time may have interrupted the recovery of marine organisms that began in the more oxic waters of the Smithian. These episodes of significant and prolonged bottom-water anoxia coincide with the most negative δ13C values, suggesting that Early Triassic perturbations to the global carbon cycle were tightly coupled to changes in ocean redox chemistry.

  14. Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

    Science.gov (United States)

    Schiffman, P.; Williams, A.E.; Evarts, R.C.

    1984-01-01

    The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock ??18O compositions decrease progressively down section (with increasing metamorphic grade): +22.4??? (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to +5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member. Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock ??18O can be best explained by isotopic exchange with discharging 18O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500??C. 18O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpellyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center. ?? 1984.

  15. Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

    Energy Technology Data Exchange (ETDEWEB)

    Schiffman, P.; Williams, A.E. (California Univ., Riverside (USA). Dept. of Earth Sciences); Evarts, R.C. (Geological Survey, Menlo Park, CA (USA))

    1984-10-01

    The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock delta/sup 18/O compositions decrease progressively down section (with increasing metamorphic grade): +22.4per mille (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to 5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member. Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock delta/sup 18/O can be best explained by isotopic exchange with discharging /sup 18/O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500/sup 0/C. /sup 18/O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpel-lyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center.

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

    Science.gov (United States)

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

    2015-04-01

    Characterization of the hafnium-tungsten systematics (182Hf decaying to 182W 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 182Hf 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 182W 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.

  17. 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.

  18. Novel insights into Fukushima nuclear accident from isotopic evidence of plutonium spread along coastal rivers.

    Science.gov (United States)

    Evrard, Olivier; Pointurier, Fabien; Onda, Yuichi; Chartin, Caroline; Hubert, Amélie; Lepage, Hugo; Pottin, Anne-Claire; Lefèvre, Irène; Bonté, Philippe; Laceby, J Patrick; Ayrault, Sophie

    2014-08-19

    The Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident led to important releases of radionuclides into the environment, and trace levels of plutonium (Pu) were detected in northeastern Japan. However, measurements of Pu isotopic atom and activity ratios are required to differentiate between the contributions of global nuclear test fallout and FDNPP emissions. In this study, we used a double-focusing sector field ICP-MS to measure Pu atom and activity ratios in recently deposited sediment along rivers draining the most contaminated part of the inland radioactive plume. Results showed that plutonium isotopes (i.e., (239)Pu, (240)Pu, (241)Pu, and (242)Pu) were detected in all samples, although in extremely low concentrations. The (241)Pu/(239)Pu atom ratios measured in sediment deposits (0.0017-0.0884) were significantly higher than the corresponding values attributed to the global fallout (0.00113 ± 0.00008 on average for the Northern Hemisphere between 31°-71° N: Kelley, J. M.; Bond, L. A.; Beasley, T. M. Global distribution of Pu isotopes and (237)Np. Sci. Total. Env. 1999, 237/238, 483-500). The results indicated the presence of Pu from FDNPP, in slight excess compared to the Pu background from global fallout that represented up to ca. 60% of Pu in the analyzed samples. These results demonstrate that this radionuclide has been transported relatively long distances (∼45 km) from FDNPP and been deposited in rivers representing a potential source of Pu to the ocean. In future, the high (241)Pu/(239)Pu atom ratio of the Fukushima accident sourced-Pu should be measured to quantify the supply of continental-originating material from Fukushima Prefecture to the Pacific Ocean.

  19. 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

    to be negative, indicating transmission via the hydrogen bond. In addition unusual long-range effects are seen. Structures, NMR chemical shifts and changes in nuclear shieldings upon deuteriation are calculated using DFT methods. Two-bond deuterium isotope effects on 13C chemical shifts are correlated......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...... with calculated OH stretching frequencies. Isotope effects on chemical shifts are calculated for systems with OH exchanged by OD. Hydrogen bond potentials are discussed. New and more soluble nitro derivatives are synthesized....

  20. 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

  1. 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.

    abundance of 18.38% and 81.17%, respectively, fractionate to the extent of 90%o, with a low of –30% in non- marine evaporite minerals (tourmalines) to a high of +60% in marine salt lake brines [3,4]. Chlorine is a major anion in crustal and magmatic... were used for the separation of boron while chlorine was separated using Shanghai No.732 and Dowex (50 x 8), conditioned with Ba(NO3) solution [13]. The isotopic measurements of boron and chlorine in the extracted samples were carried out...

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

    DEFF Research Database (Denmark)

    Olsen, M.B.; Schiller, Martin; Krot, A.N.

    2013-01-01

    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...... planetesimals. The inferred μMg* value of -3.87 ± 0.93 ppm for the CB parent body is significantly lower than the bulk solar system value of 4.5 ± 1.1 ppm inferred from CI chondrites, suggesting that CB chondrites accreted material comprising an early formed Al-free component. © 2013. The American Astronomical...

  3. 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

    correlated to their stable Mg-isotope composition (μ25Mg), indicating that the correlated variability was imparted by a volatility-controlled process (evaporation/condensation). The mass-independent 26Mg composition (μ26Mg*) of chondrules is consistent with single stage formation from an initially...... in the impact-generated plume of colliding planetesimals. The inferred μ26Mg* value of –3.87 ± 0.93 ppm for the CB parent body is significantly lower than the bulk solar system value of 4.5 ± 1.1 ppm inferred from CI chondrites, suggesting that CB chondrites accreted material comprising an early formed 26Al...

  4. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment

    Science.gov (United States)

    DesMarais, David J.; Strauss, Harald; Summons, Roger E.; Hayes, J. M.

    1992-01-01

    The oxidation of the Earth's crust and the increase in atmospheric oxygen early in Earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.

  5. Iron isotopes in a soil chronosequence: evidence of fractionation due to biological lifting of iron

    Science.gov (United States)

    Schulz, M. S.; Bullen, T. D.; White, A. F.; Fitzpatrick, J.

    2009-12-01

    The evolution of iron distribution with landform exposure time was studied in a marine terrace chronosequence northwest of Santa Cruz, California. The abundance of soil Fe increases with terrace age on the five terraces studied (65 to 226 Ka). Mass change calculations for Fe, indicate that not only is iron concentrated near the surface but, it is also depleted at depths >1.5m. The surficial Fe concentration cannot be fully accounted for by weathering and compaction of the soil profile or by the addition of iron content through eolian deposition to the soils. The terrace regoliths were generally unsaturated and aerobic, thus lateral movement of large amounts of dissolved reduced iron is unlikely. We propose that plant roots and symbiotic fungi (mycorrhizae) have transported iron from deep within the regolith to the shallow soil through the process of biolifting. Iron is a plant micronutrient; and unlike other mineral nutrients, it is relatively insoluble in aerobic soil solutions. Once Fe is released from decaying organic matter, the Fe-oxides are incorporated into the shallow soil. The Fe content of the current grassland vegetation was measured and yearly biomass Fe uptake calculated. The yearly cycling of plant-utilized Fe in above ground biomass multiplied by the age of the terrace is roughly equivalent to the shallow iron content of these soils. It has been shown that plants which use the strategy I Fe uptake process fractionate light Fe (Guelke and Von Blankenburg, ES&T, p1896; 2007). To test the biolifting hypothesis, Fe isotope ratios were determined for bulk soil samples from several soil depths of terraces 1 through 3 and terrace 5. The shallow soils generally have increasingly lighter δ56/54Fe with terrace age. The δ 56/54Fe values at 10cm soil depth are: 0.546, 0.628 0.381 and 0.182. The deep soil samples (>3 m) have a relatively constant isotopic composition ranging from 0.595 to 0.678 δ 56/54Fe. The deep sample ratios are between the values of the

  6. Lead Contamination in Cocoa and Cocoa Products: Isotopic Evidence of Global Contamination

    OpenAIRE

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

    2005-01-01

    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 ≤ 0.5 ng/g, which is one of the lowest reported values for a natural food. In contrast, lead concentrations of manufactured cocoa and chocolate products were as high as 230 and 70 ng/g, respectively, which are consistent with mark...

  7. Important Crustal Growth in the Phanerozoic: Isotopic Evidence of Granitoids from East-Central Asia

    Indian Academy of Sciences (India)

    Bor-ming Jahn; Fuyuan Wu; Dawei Hong

    2000-03-01

    The growth of the continental crust is generally believed to have been essentially completed in the Precambrian, and the amount of juvenile crust produced in the Phanerozoic is considered insignificant. Such idea of negligible growth in the Phanerozoic is now challenged by the revelation of very large volume of juvenile crust produced in the period of 500 to 100 Ma in several orogenic belts. While appreciable volumes of juvenile terranes in North America (Canadian Cordillera, Sierra Nevada and Peninsular Range, Appalachians) have been documented 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. New and published Nd-Sr isotope data indicate that the Phanerozoic granitoids from the southern belt of the ECAOB (Xinjiang-West Mongolia-Inner Mongolia-NE China) as well as from Mongolia and Transbaikalia were generated from sources dominated by a depleted mantle component. These granitoids represent a significant growth of juvenile crust in the Phanerozoic. Although most plutons in this huge orogenic belt belong to the calc-alkaline series, the ECAOB is also characterized by the emplacement of voluminous A-type granites. The origin of these rocks is probably multiple and is still widely debated. However, the isotopic data (Sr-Nd-O) and trace element abundance patterns of A-type granites from the ECAOB clearly indicate their mantle origin. The evolution of the ECAOB and the entire Altaid Collage is most likely related to successive accretion of arc complexes. However, the emplacement of a large volume of post-tectonic A-type granites requires another mechanism, probably through a series of processes including underplating of massive basaltic magma, partial melting of these basic rocks to produce granitic liquids, followed by extensive fractional crystallization. The proportion of juvenile to recycled, as well as

  8. Effects of carbonate leaching on foraminifer stable isotopes ratios

    Science.gov (United States)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  9. The Evaporation Effect on the Isotopes in the Yellow River Water

    Institute of Scientific and Technical Information of China (English)

    SU Xiaosi; LIN Xueyu; LIAO Zisheng; WANG Jinsheng

    2001-01-01

    Based on the isotope analysis result of water samples in the 18 sections of the Yellow River, the variation of δ18Oand δD have been analyzed. From near the source to the entrance to the sea, the Yellow River has a general trend that the ratios of the stable isotope increase progressively; The main factors affecting the isotopes in the river water are mixing of external water bodies, evaporation and others; In the river segment between Lanzhou and Baotou and in lower reaches, the extent of the evaporation effect on the isotope fractionation from the river water surface is limited but the evaporation from the irrigated river water and the return flow is one of the main factors affecting the isotopes in river water.

  10. Chemical and isotopic evidence of nitrogen transformation in the Mississippi River, 1997-98

    Science.gov (United States)

    Battaglin, William A.; Kendall, Carol; Chang, Cecily C. Y.; Silva, Steven R.; Campbell, D. H.

    2001-05-01

    An Erratum has been published for this article in Hydrological Processes 16(5) 2002, 1129-1130.Nitrate (NO3) and other nutrients discharged by the Mississippi River are suspected of causing a zone of depleted dissolved oxygen (hypoxic zone) in the Gulf of Mexico each summer. The hypoxic zone may have an adverse affect on aquatic life and commercial fisheries. The amount of NO3 delivered by the Mississippi River to the Gulf of Mexico is well documented, but the relative contributions of different sources of NO3, and the magnitude of subsequent in-stream transformations of NO3, are not well understood. Forty-two water samples collected in 1997 and 1998 at eight stations located either on the Mississippi River or its major tributaries were analysed for NO3, total nitrogen (N), atrazine, chloride concentrations and NO3 stable isotopes (15N and 18O). These data are used to assess the magnitude and nature of in-stream N transformation and to determine if the 15N and Thebes, IL. In both Lagrangian sets, mass-balance calculations indicate only a small amount of in-stream N loss. The stable isotope data from the samples suggest that in-stream N assimilation and not denitrification accounts for most of the N loss in the lower Mississippi River during the spring and early summer months. Published in 2001 by John Wiley & Sons, Ltd.

  11. Isotopic evidence from the eastern Canadian shield for geochemical discontinuity in the proterozoic mantle

    Science.gov (United States)

    Ashwal, L.D.; Wooden, J.L.

    1983-01-01

    Most workers agree that Proterozoic anorthosite massifs represent the crystallization products of mantle-derived magmas1,2, although the composition of the parental melts is a major unsolved petrological problem 3. As mantle-derived rocks, the massifs can be used as geochemical probes of their late Precambrian upper mantle sources. We report here Nd and Sr isotopic compositions of anorthosites and related rocks from the Grenville and Nain Provinces of the eastern Canadian shield. Here 75% of the Earth's known anorthosite is found in a 1,600-km belt from the Adirondack Mountains of northern New York State to the eastern coast of Labrador4 (Fig. 1). The results indicate that the massifs were derived from at least two distinct mantle source regions which were established before 1,650 Myr ago, and were episodically involved in magmatism over ???500 Myr. One reservoir, below the Grenville Province, and probably below much of the eastern Superior Province, was isotopically similar to the depleted, modern-day mid-ocean ridge basalt (MORB) source. The other reservoir was chondritic to moderately enriched, and is most easily identified in the Nain Province, but may have occurred scattered throughout the Superior Province. ?? 1983 Nature Publishing Group.

  12. 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.

  13. 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.

  14. Food sources of the Manila clam Ruditapes philippinarum in intertidal areas: evidence from stable isotope analysis

    Institute of Scientific and Technical Information of China (English)

    ZHAO Liqiang; YAN Xiwu; YANG Feng

    2013-01-01

    Based on stable isotope analysis,we characterized the dietary regime of the Manila clam Ruditapesphilippinarum inhabiting intertidal areas along the Liaodong Peninsula,Northern China.Samples,including particulate organic matter (POM; n=30),benthic microalgae (BMI; n=30) and R.philippinarum (n=60),were collected from six sampling sites displaying the same ecological conditions.Of the two primary food sources,POM was more depleted in δ13C (-20.61‰ to-22.89‰) than BMI was (-13.90‰ to-16.66‰).With respect to 15N,BMI was more enriched (2.90‰ to 4.07‰) than POM was (4.13‰ to 5.12‰).The δ13C values of R.philippinarum ranged from-18.78‰ to-19.35‰ and the δ15N values from 7.96‰ to 8.63‰,which were intermediate between the POM and BMI values.In a two-source isotope mixing model,we estimated the relative contributions of POM and BMI to the diet of R.philippinarum to be 74.2% and 25.8%,respectively.We conclude that R.philippinarum feeds mainly on POM,and BMI is also an important supplemental food source in intertidal areas.

  15. Campanian Climatic Change: Isotopic Evidence from Far East, North America, North Atlantic and Western Europe

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Paleoclimatic settings have been reconstructed for the Campanian using original oxygenisotopic analyses of well-preserved molluskan and foraminifera shells from Russian Far East,Hokkaido, USA, Belgium and some DSDP holes (95, 98, 102, 390A, and 392A) in North Atlantic. Early Early Campanian climatic optimum has been recognized from data on high bottom shelf water paleotemperatures in middle latitudes of both the western circum-Pacific (to 24.2℃) and the eastern circum-Pacific (to 26.4℃) areas and high bottom shallow water paleotemperatures in high latitudes of the Koryak Upland (22.4-25.5℃), which agrees with the data on the Campanian Barykovskaya flora in high latitudes (Golovneva and Herman, 1998) and Jonker flora and its equivalents in middle latitudes. Judging from the data on comparatively high bottom shallow water paleotemperature values in high latitudes, South Alaska (19.4℃) and the Koryak Upland (22.4-25.5℃), we also expect Latest Campanian temperature maximum, which has not been confirmed, however, for low and middle latitudes by neither of isotopic nor paleobotanic data now. Main climatic tendency during the Campanian (with the exception of Latest Campanian) has been learned from isotopic composition of Campanian aragonitic ammonoid shells from the Hokkaido-South Sakhalin (Krilyon) marine basin.In contrary to Huber's et al. (2002) assumption, we expect warm greenhouse conditions during the most part of the Campanian.

  16. Paleosol Stable Isotope Evidence for Early Hominid Occupation of East Asian Temperate Environments

    Science.gov (United States)

    Wang, Hong; Ambrose, Stanley H.; Liu, Chao-Li Jack; Follmer, Leon R.

    1997-09-01

    Hominids left Africa and occupied mainland Asia by 1.8 myr ago. About 1.15 myr ago Homo erectusand an associated Stegodon-Ailuropodafauna migrated from subtropical China across the Qinling Mountains into the temperate Loess Plateau. This migration may be an evolutionary milestone in human adaptability because it may represent the first occupation of a nontropical environment. Loess-paleosol stable isotope ratios from the last interglacial-glacial cycle provide comparative data for reconstructing the hominid paleoenvironments. The climate during Gongwangling hominid occupation about 1.15 myr ago was influenced by both Siberian-Mongolian winter and Indian summer monsoon systems characterized as a cold/cool, dry winter and warm/mild, semihumid summer and fall. The Gongwangling hominids preyed mainly on warm-climate-adapted animals such as Stegodon-Ailuropodafauna, suggesting a warm season occupation. The stable isotope ratios also indicate that the Chenjiawo hominids occupied an environment similar to that of the Gongwangling about 650,000 yr ago. The associated fauna, with a mixture of forest and steppe, warm- and cold/cool-climate-adapted animal assemblage's, suggests a permanent occupation by this time. Thus, the reliable earliest and permanent occupation of temperate environments may have occurred 150,000 yr earlier in eastern Asia rather than in Europe.

  17. Stable isotope evidence for trophic overlap of sympatric Mexican Lake Chapala silversides (Teleostei: Atherinopsidae: Chirostoma spp.

    Directory of Open Access Journals (Sweden)

    Norman Mercado-Silva

    Full Text Available We explore the trophic role that a diverse sympatric group of fishes in the genus Chirostoma play in a large, shallow lake in central Mexico, Lake Chapala. We use δ13C and δ15N stable isotope - based food web analyses to explore how they relate to other components of the Lake Chapala ecosystem. We find five Chirostoma species in top trophic levels of the Chapala food web compared to other fishes, relying on a combination of zooplankton, fish and benthic resources as energy sources. Food web metric analyses showed generally overlapping trophic niches for members of Chirostoma, especially in terms of δ13C. However, C. jordani had lower mean δ15N isotopic values than C. promelas. As a group, "pescados blancos" (C. sphyraena and C. promelas also had higher δ15N signatures than "charales" (C. consocium, C. jordani and C. labarcae reflecting greater piscivory, but these differences were not strong for all food web metrics used. Trophic overlap among species of Chirostoma in Lake Chapala raises questions about the forces that might have led to a morphologically diverse but functionally similar and monophyletic group of species.

  18. Evidence of atmospheric sulphur in the martian regolith from sulphur isotopes in meteorites.

    Science.gov (United States)

    Farquhar, J; Savarino, J; Jackson, T L; Thiemens, M H

    2000-03-02

    Sulphur is abundant at the martian surface, yet its origin and evolution over time remain poorly constrained. This sulphur is likely to have originated in atmospheric chemical reactions, and so should provide records of the evolution of the martian atmosphere, the cycling of sulphur between the atmosphere and crust, and the mobility of sulphur in the martian regolith. Moreover, the atmospheric deposition of oxidized sulphur species could establish chemical potential gradients in the martian near-surface environment, and so provide a potential energy source for chemolithoautotrophic organisms. Here we present measurements of sulphur isotopes in oxidized and reduced phases from the SNC meteorites--the group of related achondrite meteorites believed to have originated on Mars--together with the results of laboratory photolysis studies of two important martian atmospheric sulphur species (SO2 and H2S). The photolysis experiments can account for the observed sulphur-isotope compositions in the SNC meteorites, and so identify a mechanism for producing large abiogenic 34S fractionations in the surface sulphur reservoirs. We conclude that the sulphur data from the SNC meteorites reflects deposition of oxidized sulphur species produced by atmospheric chemical reactions, followed by incorporation, reaction and mobilization of the sulphur within the regolith.

  19. Isotopic Evidence of a Sedimentary Carbon Source at the Endeavour Hydrothermal System, a Potential Site of Microbial Methane Oxidation

    Science.gov (United States)

    Proskurowski, G. K.; Lilley, M. D.; Brown, T. A.

    2002-12-01

    The hydrothermal systems on the Endeavour Segment of the Juan de Fuca Ridge have long been characterized as "bare rock hosted", as there is no sediment cover at Endeavour. However, chemical evidence in the form of anomalously high methane, ammonia and various trace metal concentrations reported in the last 10 years are consistent with a sediment source at Endeavour. Here we present a unique data set of stable and radiocarbon isotopic measurements made on CO2 from Endeavour hydrothermal vent fluids. When plotted against each other, a linear relationship between δ13CO2 and CO2 fraction modern values, suggests mixing of two CO2 sources. The data supports a mixing model between a -5.4\\permil, radiocarbon dead magmatic endmember, and a -17.8\\permil, 18,500 year old carbon source. The second endmember corresponds extremely well with stable isotopic measurements made on carbonate nodules from sediments at ODP drill sites on Middle Valley, a sedimented hydrothermal site 40km North of the Endeavour Segment. These sediments were emplaced during turbidite flows in the late Pleistocene, nominally 20,000 years ago. The mixing model suggests that about 20% of the CO2 found in Endeavour hydrothermal vent fluids is from this sedimentary endmember. We propose that the observed sedimentary signal is incorporated as heated hydrothermal fluids migrate upwards beneath the ridge axis through a zone of buried sediments. An alternative explanation is that there is a hydrologic link between Middle Valley and Endeavour, and that the sedimentary signal is imported from observed sediments at Middle Valley. Sediments provide labile sources of carbon that may be incorporated into microbial metabolic pathways. Sediments at Middle Valley exhibit strongly depleted δ13CO2 values (between -27 and -44\\permil) suggesting microbial fractionation, most likely anaerobic methane oxidation. While microbial methane oxidation is likely an active process in sediments at Middle Valley, isotopic evidence

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

    Science.gov (United States)

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

    2006-01-01

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

  1. 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

  2. High continental weathering rate during Early Cambrian: Evidence from Os isotopic composition of Early Cambrian Ocean

    Science.gov (United States)

    Jiang, S.-Y.; Yang, J.-H.; Ling, H.-F.; Feng, H.-Z.; Chen, Y.-Q.; Chen, J.-H.

    2003-04-01

    The paleo-ocean environmental change during the Precambrian-Cambrian transition is a key issue related to the causes for an explosive radiation of different metazoan phyla during Early Cambrian. The chemical and isotopic compositions of marine sediments and chemical precipitates such as carbonates, phosphorites, siliceous rocks, and black shales record the changing composition and physical conditions of the seawater in which these rocks accumulated. Organic carbon-rich black shales from marine environments are commonly enriched in a number of trace elements such as Ni, Mo, V, Co, Cr, Au, U, As, Pb, Zn, Cu, Re, and platinum-group-elements (PGE). Recent researches have demonstrated that Re-Os isotopes and PGE contents in black shales are useful proxies for seawater chemistry. It is believed that Re and Os in orgainc-carbon rich black shales are mostly hydrogeneous in origin which were largely sequestered from seawater at the time of deposition. In South China, the Lower Cambrian black shale sequence of the Niutitang Formation (and lateral equivalents) exists broadly several thousands kilometers. The lowermost sequence of this formation contain a thin sulfide ore horizon with an apparently unique and extreme case of metal enrichments such as Mo, Ni, Se, Re, Os, As, Hg, Sb, Ag, Au, Pt, and Pd. In this study, we conducted a preliminary investigation of Re-Os isotopes and Plantium Group Element (PGE) distribution patterns of the balck shales and intercalated Ni-Mo polymetallic sulfide bed from Guizhou and Hunan Provinces. The high rOs(t) values of the black shales indicate that the Early Cambrian ocean in Yangtze Platform had a highly radiogenic Os, possibly as a result of high continental weathering rate at that time. The Ni-Mo polymetallic sulfide ores within the black shales have lower rOs(t) values than the black shales, and they show similar REE and PGE patterns as the hydrothermal siliceous rocks within the Lower Cambrian strata, which suggest that the Ni

  3. 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......” and tautomeric systems. Isotope effects on chemical shifts are particularly useful in such studies. All kinds of intramolecular hydrogen bonded systems will be treated, typical hydrogen bond donors: OH, NH, SH and NH+, typical acceptors C=O, C=N, C=S C=N−. The paper will be deal with both secondary and primary...... isotope effects on chemical shifts. These two types of isotope effects monitor the same hydrogen bond, but from different angles...

  4. Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111).

    Science.gov (United States)

    Koitaya, Takanori; Shimizu, Sumera; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2012-06-07

    Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.

  5. 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

    2016-08-01

    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.

  6. 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.

  7. Deformation effects on cluster decays of radium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Soylu, A., E-mail: asimsoylu@gmail.com; Evlice, S.

    2015-04-15

    We systematically investigate the influence of nuclear deformations of the cluster and daughter nuclei on the half-lives of {sup 4}He, {sup 8,10}Be, {sup 12,14,16}C and {sup 16,18,20,22}O cluster decays from {sup 210–226}Ra. The Wentzel–Kramers–Brillouin (WKB) method and Bohr–Sommerfeld quantization condition with the deformed squared Woods–Saxon and Cosh potentials are used phenomenologically in order to compute the half-lives. The calculations are performed for the spherical cluster and deformed daughter, deformed cluster and spherical daughter and deformed cluster and daughter cases. The half-lives for different orientation angles as well as over all angles are calculated, in order to show the deformation effects on the systems. In cases where the deformation of both cluster and daughter effect the result, it is found that the deformation of the cluster is more important than the deformation of the daughter. Furthermore, it is also found that taking into account the orientation angles of the daughter and cluster also improves the results when compared to experiment. However, the results for a Cosh potential with certain parameters without any deformation are found to be more compatible with both the results obtained by the Coulomb and proximity potential model (CPPM) and the universal formula for cluster decay (UNIV), as well as the experimental values for {sup 4}He and {sup 14}C decays. The results provide a useful method for estimating the unknown experimental half-lives of possible exotic decays from Ra isotopes.

  8. Deformation effects on cluster decays of radium isotopes

    Science.gov (United States)

    Soylu, A.; Evlice, S.

    2015-04-01

    We systematically investigate the influence of nuclear deformations of the cluster and daughter nuclei on the half-lives of 4He, 8,10Be, 12,14,16C and 16,18,20,22O cluster decays from 210-226Ra. The Wentzel-Kramers-Brillouin (WKB) method and Bohr-Sommerfeld quantization condition with the deformed squared Woods-Saxon and Cosh potentials are used phenomenologically in order to compute the half-lives. The calculations are performed for the spherical cluster and deformed daughter, deformed cluster and spherical daughter and deformed cluster and daughter cases. The half-lives for different orientation angles as well as over all angles are calculated, in order to show the deformation effects on the systems. In cases where the deformation of both cluster and daughter effect the result, it is found that the deformation of the cluster is more important than the deformation of the daughter. Furthermore, it is also found that taking into account the orientation angles of the daughter and cluster also improves the results when compared to experiment. However, the results for a Cosh potential with certain parameters without any deformation are found to be more compatible with both the results obtained by the Coulomb and proximity potential model (CPPM) and the universal formula for cluster decay (UNIV), as well as the experimental values for 4He and 14C decays. The results provide a useful method for estimating the unknown experimental half-lives of possible exotic decays from Ra isotopes.

  9. Feldspar palaeo-isochrons from early Archaean TTGs: Pb-isotope evidence for a high U/Pb terrestrial Hadean crust

    Science.gov (United States)

    Kamber, B. S.; Whitehouse, M. J.; Moorbath, S.; Collerson, K. D.

    2001-12-01

    Feldspar lead-isotope data for 22 early Archaean (3.80-3.82 Ga) tonalitic gneisses from an area south of the Isua greenstone belt (IGB),West Greenland, define a steep linear trend in common Pb-isotope space with an apparent age of 4480+/-77 Ma. Feldspars from interleaved amphibolites yield a similar array corresponding to a date of 4455+/-540 Ma. These regression lines are palaeo-isochrons that formed during feldspar-whole rock Pb-isotope homogenisation a long time (1.8 Ga) after rock formation but confirm the extreme antiquity (3.81 Ga) of the gneissic protoliths [1; this study]. Unlike their whole-rock counterparts, feldspar palaeo-isochrons are immune to rotational effects caused by the vagaries of U/Pb fractionation. Hence, comparison of their intercept with mantle Pb-isotope evolution models yields meaningful information regarding the source history of the magmatic precursors. The locus of intersection between the palaeo-isochrons and terrestrial mantle Pb-isotope evolution lines shows that the gneissic precursors of these 3.81 Ga gneisses were derived from a source with a substantially higher time-integrated U/Pb ratio than the mantle. Similar requirements for a high U/Pb source have been found for IGB BIF [2], IGB carbonate [3], and particularly IGB galenas [4]. Significantly, a single high U/Pb source that separated from the MORB-source mantle at ca. 4.3 Ga with a 238U/204Pb of ca. 10.5 provides a good fit to all these observations. In contrast to many previous models based on Nd and Hf-isotope evidence we propose that this reservoir was not a mantle source but the Hadean basaltic crust which, in the absence of an operating subduction process, encased the early Earth. Differentiation of the early high U/Pb basaltic crust could have occurred in response to gravitational sinking of cold mantle material or meteorite impact, and produced zircon-bearing magmatic rocks. The subchondritic Hf-isotope ratios of ca. 3.8 Ga zircons support this model [5] provided that

  10. Diets of impala from Kruger National Park: evidence from stable carbon isotopes

    Directory of Open Access Journals (Sweden)

    M. Sponheimer

    2003-12-01

    Full Text Available Impala are known to exhibit dietary flexibility, relying primarily on browse in some areas and graze in others. In this study we use stable isotope analysis of faeces and hair to examine the diets of Impala in Kruger National Park. As expected, the data show that Impala are mixed-feeders and highly distinct from grazing buffalo and browsing kudu. Moreover, Impala, Buffalo, and Kudu faeces contain 2.1 %, 1.4 %, and 2.9 % nitrogen respectively, suggesting that Impala diets are of intermediate quality. There are also marked differences between Impala populations in the northern and southern regions of the park. The northern Impala graze less than their southern counterparts. This difference probably reflects decreased availability of herbaceous forage in the mopane-dominated north. Males and females also have different diets, with males grazing more than females.

  11. Oxygen isotope analysis of human bone phosphate evidences weaning age in archaeological populations.

    Science.gov (United States)

    Britton, Kate; Fuller, Benjamin T; Tütken, Thomas; Mays, Simon; Richards, Michael P

    2015-06-01

    Here we report bone phosphate oxygen (δ(18)Op) values from perinates/neonates and infants (isotope systems likely due to breastfeeding. After the age of 2-3 years, δ(18)Op values are lower, and all children between the ages of 4 and 12, along with the vast majority of sub-adults and adults sampled (aged 16 to >50 years), have δ(18)Op values consistent with the consumption of local modern drinking water. The implications of this study for the reconstruction of weaning practices in archaeological populations are discussed, including variations observed with bone δ(15)Ncoll and δ(18)Op co-analysis and the influence of culturally-modified drinking water and seasonality. The use of this method to explore human mobility and palaeoclimatic conditions are also discussed with reference to the data presented. © 2015 Wiley Periodicals, Inc.

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

    Science.gov (United States)

    Böhlke, John Karl; Hatzinger, Paul B; Sturchio, Neil C; Gu, Baohua; Abbene, Irene; Mroczkowski, Stanley J

    2009-08-01

    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 has been largely circumstantial. Here we report ClO4- stable isotope data (delta37Cl, delta18O, and delta17O), 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 with groundwater age, possibly because of decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO3- fertilizers in recent years. Because ClO4-/NO3- ratios of Atacama NO3- fertilizers imported in the past (approximately 2 x 10(-3) mol mol(-1)) were much higher than the CO4-/NO3- ratio of recommended drinking-water limits (7 x 10(-5) mol mol(-1) in New York), ClO4- could exceed drinking-water 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.

  13. Kinetic and solvent deuterium isotope effects in the oxidation of putrescine catalysed by enzyme diamine oxidase.

    Science.gov (United States)

    Pałka, Katarzyna; Szymańska, Jolanta; Kańska, Marianna

    2013-01-01

    In this study, the kinetic isotope effects and solvent isotope effects in the reaction of the deamination of [(1R)-(2)H ] putrescine--catalysed by enzyme diamine oxidase (EC 1.4.3.6)--were determined using a non-competitive spectroscopic method. Putrescine, stereospecifically labelled with deuterium, was obtained by enzymatic decarboxylation of l-ornithine that was carried out in a fully deuteriated incubation medium.

  14. 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.

  15. Diffuse migratory connectivity in two species of shrubland birds: evidence from stable isotopes

    Science.gov (United States)

    Knick, Steven T.; Leu, Matthias; Rotenberry, John T.; Hanser, Steven E.; Fesenmyer, Kurt A.

    2014-01-01

    Connecting seasonal ranges of migratory birds is important for understanding the annual template of stressors that influence their populations. Brewer’s sparrows (Spizella breweri) and sagebrush sparrows (Artemisiospiza nevadensis) share similar sagebrush (Artemisia spp.) habitats for breeding but have different population trends that might be related to winter location. To link breeding and winter ranges, we created isoscapes of deuterium [stable isotope ratio (δ) of deuterium; δ2H] and nitrogen (δ15N) for each species modeled from isotope ratios measured in feathers of 264 Brewer’s and 82 sagebrush sparrows and environmental characteristics at capture locations across their breeding range. We then used feather δ2Hf and δ15Nf measured in 1,029 Brewer’s and 527 sagebrush sparrows captured on winter locations in southwestern United States to assign probable breeding ranges. Intraspecies population mixing from across the breeding range was strong for both Brewer’s and sagebrush sparrows on winter ranges. Brewer’s sparrows but not sagebrush sparrows were linked to more northerly breeding locations in the eastern part of their winter range. Winter location was not related to breeding population trends estimated from US Geological Survey Breeding Bird Survey routes for either Brewer’s or sagebrush sparrows. Primary drivers of population dynamics are likely independent for each species; Brewer’s and sagebrush sparrows captured at the same winter location did not share predicted breeding locations or population trends. The diffuse migratory connectivity displayed by Brewer’s and sagebrush sparrows measured at the coarse spatial resolution in our analysis also suggests that local environments rather than broad regional characteristics are primary drivers of annual population trends.

  16. Evidence of a dynamic microbial community structure and predation through combined microbiological and stable isotope characterization

    Science.gov (United States)

    Druhan, J. L.; Bill, M.; Lim, H. C.; Wu, C.; Conrad, M. E.; Williams, K. H.; DePaolo, D. J.; Brodie, E.

    2014-12-01

    The speciation, reactivity and mobility of carbon in the near surface environment is intimately linked to the prevalence, diversity and dynamics of native microbial populations. We utilize this relationship by introducing 13C-labeled acetate to sediments recovered from a shallow aquifer system to track both the cycling of carbon through multiple redox pathways and the associated spatial and temporal evolution of bacterial communities in response to this nutrient source. Results demonstrate a net loss of sediment organic carbon over the course of the amendment experiment. Furthermore, these data demonstrated a source of isotopically labeled inorganic carbon that was not attributable to primary metabolism by acetate-oxidizing microorganisms. Fluid samples analyzed weekly for microbial composition by pyrosequencing of ribosomal RNA genes showed a transient microbial community structure, with distinct occurrences of Azoarcus, Geobacter and multiple sulfate reducing species over the course of the experiment. In combination with DNA sequencing data, the anomalous carbon cycling process is shown to occur exclusively during the period of predominant Geobacter species growth. Pyrosequencing indicated, and targeted cloning and sequencing confirmed the presence of several bacteriovorous protozoa, including species of the Breviata, Planococcus and Euplotes genera. Cloning and qPCR analysis demonstrated that Euplotes species were most abundant and displayed a growth trajectory that closely followed that of the Geobacter population. These results suggest a previously undocumented secondary turnover of biomass carbon related to protozoan grazing that was not sufficiently prevalent to be observed in bulk concentrations of carbon species in the system, but was clearly identifiable in the partitioning of carbon isotopes. The impact of predator-prey relationships on subsurface microbial community dynamics and therefore the flux of carbon through a system via the microbial biomass

  17. The origin of aubrites: Evidence from lithophile trace element abundances and oxygen isotope compositions

    Science.gov (United States)

    Barrat, J. A.; Greenwood, R. C.; Keil, K.; Rouget, M. L.; Boesenberg, J. S.; Zanda, B.; Franchi, I. A.

    2016-11-01

    We report the abundances of a selected set of "lithophile" trace elements (including lanthanides, actinides and high field strength elements) and high-precision oxygen isotope analyses of a comprehensive suite of aubrites. Two distinct groups of aubrites can be distinguished: (a) the main-group aubrites display flat or light-REE depleted REE patterns with variable Eu and Y anomalies; their pyroxenes are light-REE depleted and show marked negative Eu anomalies; (b) the Mount Egerton enstatites and the silicate fraction from Larned display distinctive light-REE enrichments, and high Th/Sm ratios; Mount Egerton pyroxenes have much less pronounced negative Eu anomalies than pyroxenes from the main-group aubrites. Leaching experiments were undertaken to investigate the contribution of sulfides to the whole rock budget of the main-group aubrites. Sulfides contain in most cases at least 50% of the REEs and of the actinides. Among the elements we have analyzed, those displaying the strongest lithophile behaviors are Rb, Ba, Sr and Sc. The homogeneity of the Δ17O values obtained for main-group aubrite falls [Δ17O = +0.009 ± 0.010‰ (2σ)] suggests that they originated from a single parent body whose differentiation involved an early phase of large-scale melting that may have led to the development of a magma ocean. This interpretation is at first glance in agreement with the limited variability of the shapes of the REE patterns of these aubrites. However, the trace element concentrations of their phases cannot be used to discuss this hypothesis, because their igneous trace-element signatures have been modified by subsolidus exchange. Finally, despite similar O isotopic compositions, the marked light-REE enrichments displayed by Mount Egerton and Larned suggest that they are unrelated to the main-group aubrites and probably originated from a distinct parent body.

  18. Are Colorado Plateau Eclogite Xenoliths Franciscan?: Oxygen Isotope Evidence From Zoned Garnet

    Science.gov (United States)

    Hoover, W. F.; Page, F. Z.; Schulze, D. J.; Kitajima, K.; Valley, J. W.

    2014-12-01

    Eclogite xenoliths from the Moses Rock diatreme, UT, USA are of controversial (Proterozoic or Phanerozoic) age. In this study, seven garnets from four Moses Rock eclogite xenoliths were analyzed for δ18O by ion microprobe. Garnet core δ18O values are 7.8-10.3‰ VSMOW. All samples have a sharp change between cores and rim values of 5.8-6.9‰. These garnets have the first reported oxygen isotope zoning from mantle xenoliths. The core values are well outside the range of garnets equilibrated with the mantle, suggesting that they began growth during subduction from an altered oceanic crustal protolith. Most rim values reach the mantle range. This decrease in δ18O from core to rim is consistent with continued subduction of the eclogites into the mantle. The failure of some garnet rims to reach mantle δ18O values may indicate that they did not equilibrate fully with the mantle, or were exposed to a mixed mantle-slab fluid. Zoning in the samples from this study record a stepped shift from an altered upper oceanic crust protolith, to a mantle-influenced environment. The preservation of zoning in some of the samples from this study suggests that these eclogites were protected within the cool subducting slab and experienced a short mantle residence time. The preservation of cation and oxygen isotope zoning is more consistent with an origin during Franciscan subduction than Proterozoic subduction, unless the zoning is a late feature that formed just prior to volcanic emplacement. This is further supported by the similar patterns of increased pyrope content and decreasing δ18O found in some Franciscan eclogite garnets (e.g., Errico et al., 2013, CMP).

  19. Evidence from isotopic geochemistry as an indicator of eutrophication of Meiliang Bay in Lake Taihu, China

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In this paper, Lake Taihu, a large shallow freshwater lake in China, is chosen as an example of reconstruction of eutrophication through the comparison between stable isotopes from dissolved nutrients and plants and water column nutrient parameters and integration of multiple proxies in a sediment core from Meiliang Bay including TN, TP, TOC, C/N, δ15N, δ13C, etc. Differences in aquatic plant species and trophic status between East Taihu Bay and Meiliang Bay are indicated by their variations in δ13C and δ15N of aquatic plants and δ15N of NH4+. A significant influence ofexternal nutrient inputs on Meiliang Bay is reflected in temporal changes in δ 15N of NH4+ and hydro-environmental parameters. The synchronous change between δ13C and δ15N values of sedimented organic matter (OM) has been attributed to elevated primary production at the beginning of eutrophication between 1950 and 1990, then recent inverse correlation between them has been caused by the uptake of 15N-enriched inorganic nitrogen by phytoplankton grown under eutrophication and subsequent OM decomposition and denitrification in surface sediments, indicating that the lake has suffered from progressive eutrophication since 1990. Based on the use of a combination of stable isotopes and elemental geochemistry, the eutrophication of Meiliang Bay in Lake Taihu could be better traced. These transitions of the lake eutrophication respectively occurring in the 1950s and 1990s have been suggested as a reflection of growing impacts of human activities, which is coincident with the instrumental data.

  20. 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.

  1. Calcium-aluminum-rich inclusions with fractionation and unidentified nuclear effects (FUN CAIs): II. Heterogeneities of magnesium isotopes and 26Al in the early Solar System inferred from in situ high-precision magnesium-isotope measurements

    Science.gov (United States)

    Park, Changkun; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Davis, Andrew M.; Bizzarro, Martin

    2017-03-01

    Calcium-aluminum-rich inclusions with isotopic mass fractionation effects and unidentified nuclear isotopic anomalies (FUN CAIs) have been studied for more than 40 years, but their origins remain enigmatic. Here we report in situ high precision measurements of aluminum-magnesium isotope systematics of FUN CAIs by secondary ion mass spectrometry (SIMS). Individual minerals were analyzed in six FUN CAIs from the oxidized CV3 carbonaceous chondrites Axtell (compact Type A CAI Axtell 2271) and Allende (Type B CAIs C1 and EK1-4-1, and forsterite-bearing Type B CAIs BG82DH8, CG-14, and TE). Most of these CAIs show evidence for excess 26Mg due to the decay of 26Al. The inferred initial 26Al/27Al ratios [(26Al/27Al)0] and the initial magnesium isotopic compositions (δ26Mg0) calculated using an exponential law with an exponent β of 0.5128 are (3.1 ± 1.6) × 10-6 and 0.60 ± 0.10‰ (Axtell 2271), (3.7 ± 1.5) × 10-6 and -0.20 ± 0.05‰ (BG82DH8), (2.2 ± 1.1) × 10-6 and -0.18 ± 0.05‰ (C1), (2.3 ± 2.4) × 10-5 and -2.23 ± 0.37‰ (EK1-4-1), (1.5 ± 1.1) × 10-5 and -0.42 ± 0.08‰ (CG-14), and (5.3 ± 0.9) × 10-5 and -0.05 ± 0.08‰ (TE) with 2σ uncertainties. We infer that FUN CAIs recorded heterogeneities of magnesium isotopes and 26Al in the CAI-forming region(s). Comparison of 26Al-26Mg systematics, stable isotope (oxygen, magnesium, calcium, and titanium) and trace element studies of FUN and non-FUN igneous CAIs indicates that there is a continuum among these CAI types. Based on these observations and evaporation experiments on CAI-like melts, we propose a generic scenario for the origin of igneous (FUN and non-FUN) CAIs: (i) condensation of isotopically normal solids in an 16O-rich gas of approximately solar composition; (ii) formation of CAI precursors by aggregation of these solids together with variable abundances of isotopically anomalous grains-possible carriers of unidentified nuclear (UN) effects; and (iii) melt evaporation of these precursors

  2. Priming effects of biochar elucidated using stable isotope techniques.

    Science.gov (United States)

    Hood-Nowotny, R.; Vanlauwe, B.

    2012-04-01

    Organic residues are routinely used in tropical agricultural systems; as mulches to reduce water losses and for their fertiliser value. The addition of high N content organic residues to soils has been promoted in tropical countries as a means to achieve sustainable intensification of tropical farming systems and increasing soil organic matter status on infertile low income farms. Improving the nutrient release from these materials could have positive feedback effects in terms of improved food security and increased organic matter return to the soil through improved crop yields. Unfortunately the fertiliser value of most organic residues is such that only 10 -20% of the available nitrogen in the residue is mineralised to plant available nitrogen and taken up by the plant in the first cropping year, dropping to less than 2% in the subsequent years; thus having marginal overall impact on crop yields. Improving the fertiliser benefit of residues by combining them with the biochar addition could lead to significant increases in crop yields, an immediately tangible benefit for farmers. The addition of charcoal in boreal forest systems has been shown to increase the rate of soil organic matter decomposition, suggesting there is a priming effect of a biochar analogue on organic matter decomposition. The priming effect is the increase in soil organic matter (SOM) decomposition rate after the addition of fresh organic matter or other compounds to soil. The implication is that is biochar if addition leads to the loss of native SOM it negates the carbon benefit of adding biochar to soil. However there could also be potential benefits of priming effects of biochar under specific circumstances, for example if biochar addition leads to the priming of freshly added organic matter breakdown it may in turn improve nutrient synchronisation and overall nutrient use efficiency. We conducted a series of experiments conducted in Kenya and Austria using stable isotope tools to look at

  3. The isotope effect in H3S superconductor

    Science.gov (United States)

    Szczęśniak, R.; Durajski, A. P.

    2017-01-01

    The experimental value of H3S a isotope coefficient decreases from 2.37 to 0.31 in the pressure range from 130 GPa to 200 GPa. We have shown that the value of 0.31 is correctly reproduced in the framework of the classical Eliashberg approach in the harmonic approximation. On the other hand, the anomalously large value of the isotope coefficient (2.37) may be associated with the strong renormalization of the normal state by the electron density of states.

  4. Stable carbon isotope evidence for tracing the diet of the host Hepialus larva of Cordyceps sinensis in the Tibetan Plateau

    Institute of Scientific and Technical Information of China (English)

    CHEN Di; YUAN JianPing; XU ShiPing; ZHOU XiaoGang; ZHANG Yan; XU XiaoMing; ZOU ZhiWen; ZHANG GuRen; WANG JiangHai

    2009-01-01

    Two types of Hepialus larvae with different diets were distinguished in the Sejila Mountain, Tibetan Plateau based on the stable carbon isotope data of the host Hepialus larva of Cordyceps sinensis and its closely adjacent tender plant roots and humus fractions. Type I is the larva chiefly fed by soil humus, and characterized by the δ13C values of -22.6‰ to -23.4‰, and more than -23.4‰ in its heads. Type Ⅱ is the larva chiefly fed by tender plant roots, and characterized by the δ13C values of -24.6‰ to -27.6‰, and less than -24.6‰, in its heads. Our result has exceeded the traditional understanding that their food sources only come from the tender plant roots, and may provide evidence for choosing cheap and high-quality foods and further establishing artificial habitats in their large-scale reproduction.

  5. Stable carbon isotope ratios in Astrangia danae : evidence for algal modification of carbon pools used in calcification

    Science.gov (United States)

    Cummings, C. E.; McCarty, H. B.

    1982-06-01

    Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ13C values ranging from -5.42 to -7.30%. revealed the expected depletion of 13C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ13C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ13C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in 13C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.

  6. Investigation of Stable C and Cl Isotope Effects of Trichloroethene and Tetrachloroethylene during Evaporation at Different Temperatures

    Institute of Scientific and Technical Information of China (English)

    Tingting Yu; Yiqun Gan; Aiguo Zhou; Kai Yu; Yunde Liu

    2014-01-01

    There are variations of reported isotope enrichment factors of chlorinated organic contaminants in evaporation processes. Trichloroethene (TCE) and tetrachloroethylene (PCE) were chosen to study carbon and chlorine isotope effects during evaporation at different temperatures. Equilibrium vapor-liquid carbon and chlorine isotope effects experiments were also conducted. In the equilibrium liquid-vapor system, the 13C was enriched but 37Cl was depleted in the vapor phase, being consistent with previous results. For evaporation average carbon isotope enrichment factor εC were +0.28‰± 0.01‰ for TCE and +0.56‰±0.09‰ for PCE at temperature from 20 to 26 ºC. Meanwhile, average chlorine isotope enrichment factor εCl were -1.33‰±0.21‰ for TCE and -1.00‰±0.00‰ for PCE. The results indicate that during evaporation the equilibrium isotope effect attenuates the magnitude of carbon isotope fractionation whereas enhances the chlorine isotope effect. Isotope fractionation during evaporation is determined by both equilibrium and kinetic factors. Chlorine isotope fractionation is influenced by the evaporation rate which is linked to temperature. When using stable isotope to investigate the behavior of chlorinated organic contaminants in groundwater with slow biodegradation rate, the isotope fractionation resulted from evaporation should be taken into consideration. Furthermore, the environment conditions such as temperature are also factors to be considered.

  7. Isotope effect in the formation of H2 from H2CO studied at the atmospheric simulation chamber SAPHIR

    NARCIS (Netherlands)

    Röckmann, T.; Walter, S.; Bohn, B.; Wegener, R.; Spahn, H.; Brauers, T.; Tillmann, R.; Schlosser, E.; Koppmann, R.; Rohrer, F.

    2010-01-01

    Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H2 was used to determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecula

  8. Substrate and Transition State Binding in Alkaline Phosphatase Analyzed by Computation of Oxygen Isotope Effects.

    Science.gov (United States)

    Roston, Daniel; Cui, Qiang

    2016-09-14

    Enzymes are powerful catalysts, and a thorough understanding of the sources of their catalytic power will facilitate many medical and industrial applications. Here we have studied the catalytic mechanism of alkaline phosphatase (AP), which is one of the most catalytically proficient enzymes known. We have used quantum mechanics calculations and hybrid quantum mechanics/molecular mechanics (QM/MM) simulations to model a variety of isotope effects relevant to the reaction of AP. We have calculated equilibrium isotope effects (EIEs), binding isotope effects (BIEs), and kinetic isotope effects (KIEs) for a range of phosphate mono- and diester substrates. The results agree well with experimental values, but the model for the reaction's transition state (TS) differs from the original interpretation of those experiments. Our model indicates that isotope effects on binding make important contributions to measured KIEs on V/K, which complicated interpretation of the measured values. Our results provide a detailed interpretation of the measured isotope effects and make predictions that can test the proposed model. The model indicates that the substrate is deformed in the ground state (GS) of the reaction and partially resembles the TS. The highly preorganized active site preferentially binds conformations that resemble the TS and not the GS, which induces the substrate to adapt to the enzyme, rather than the other way around-as with classic "induced fit" models. The preferential stabilization of the TS over the GS is what lowers the barrier to the chemical step.

  9. Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)

    Science.gov (United States)

    Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.

    1998-07-01

    Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

  10. Mechanism of the flame ionization detector. II. Isotope effects and heteroatom effects

    DEFF Research Database (Denmark)

    Holm, Torkil

    1997-01-01

    The relative molar flame ionization detecton (FID) response (RMR) for a hydrocarbon does not change when deuterium is substituted for hydrogen. The exception is methane for which an inverse deuterium effect of 3..5% is observed for tetradeuteriomethane. [13C]Methane shows an inverse isotope effect...... of 2%. The reason for the small or non-existent isotope effects is that H/2H exchange takes place in the pre-combustion hydrogenolysis in the flame. This was shown by taking samples from the lower part of the flame by means of a fused silica capillary probe. By the same technique the hydrogenolytic...... reactions in the hydrogen flame of compounds added to the hydrogen gas in low concentrations were followed. Alcohols, ethers, ketones, and esters all produced methane and carbon monoxide, while amines produced methane and hydrogen cyanide, halogen compounds methane and hydrogen halide, etc. The FID response...

  11. 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

  12. 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.

  13. Stable isotope studies

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. Ionic liquids as novel stationary phases in gas liquid chromatography: inverse or normal isotope effect?

    Science.gov (United States)

    Schmarr, Hans-Georg; Slabizki, Petra; Müntnich, Sabrina; Metzger, Carmen; Gracia-Moreno, Elisa

    2012-12-28

    The separation of deuterated and non-deuterated compounds in gas liquid partitioning chromatography (GLC) on silicone type stationary phase usually results in the inverse isotope effect. With ionic liquids (ILs) as stationary phase, however, this may show a totally different nature. The inverse isotope effect, in which heavier (deuterated) isotopic compounds (isotopologues) elute earlier, is to be expected when van der Waals (London) dispersion forces play a dominant role in the solute-stationary phase interaction. Such (apolar) interactions seem to play only a minor role when ILs are the stationary phases, leading to only a marginal inverse isotope effect, e.g. for the separation of 2,4,6-trichloroanisole and its [(2)H(5)]-isotopologue on 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethansulfonyl) amide (commercialized as SLB-IL59, Supelco). Indeed, with the most polar stationary phase available (commercialized as SLB-IL111; Supelco), this separation showed a normal isotope effect. Further examples are presented and the nature of the isotope effect observed is discussed.

  15. Copper isotope effect in serum of cancer patients. A pilot study.

    Science.gov (United States)

    Télouk, Philippe; Puisieux, Alain; Fujii, Toshiyuki; Balter, Vincent; Bondanese, Victor P; Morel, Anne-Pierre; Clapisson, Gilles; Lamboux, Aline; Albarede, Francis

    2015-02-01

    The isotope effect describes mass-dependent variations of natural isotope abundances for a particular element. In this pilot study, we measured the (65)Cu/(63)Cu ratios in the serums of 20 breast and 8 colorectal cancer patients, which correspond to, respectively, 90 and 49 samples taken at different times with molecular biomarker documentation. Copper isotope compositions were determined by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). When compared with the literature data from a control group of 50 healthy blood donors, abundances of Cu isotopes predict mortality in the colorectal cancer group with a probability p = 0.018. For the breast cancer patients and the group of control women the probability goes down to p = 0.0006 and the AUC under the ROC curve is 0.75. Most patients considered in this preliminary study and with serum δ(65)Cu lower than the threshold value of -0.35‰ (per mil) did not survive. As a marker, a drop in δ(65)Cu precedes molecular biomarkers by several months. The observed decrease of δ(65)Cu in the serum of cancer patients is assigned to the extensive oxidative chelation of copper by cytosolic lactate. The potential of Cu isotope variability as a new diagnostic tool for breast and colorectal cancer seems strong. Shifts in Cu isotope compositions fingerprint cytosolic Cu chelation by lactate mono- and bidentates. This simple scheme provides a straightforward explanation for isotopically light Cu in the serum and isotopically heavy Cu in cancer cells: Cu(+) escaping chelation by lactate and excreted into the blood stream is isotopically light. Low δ(65)Cu values in serum therefore reveal the strength of lactate production by the Warburg effect.

  16. Quasi-harmonic calculations of the isotope effect in diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Harding, J.H.

    1986-11-10

    It is shown how the kinetic energy factor for isotope diffusion may be calculated within the quasi-harmonic approximation using methods devised to calculate the vibrational contribution to defect entropies. The results are compared with experiment in the cases of CoO and NiO and good agreement found.

  17. 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

  18. 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

  19. 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

  20. Sedimentary nitrate reduction and its effect on the N-isotopic composition of oceanic nitrate

    Science.gov (United States)

    Lehmann, M. F.; Sigman, D. M.; McCorkle, D. C.

    2005-12-01

    A prerequisite for assessing denitrification fluxes in a specific environment using water column nitrate N isotope ratios is the knowledge of the expressed N isotope effects of water column and/or benthic denitrification in this environment. Here, we aim at assessing the effects of benthic nitrogen cycling on the N isotopic composition of the oceanic nitrate pool in deep-sea sediments, which are believed to harbour a large portion of the global benthic denitrification. We report 15N/14N ratios of pore water nitrate in pelagic sediments from the deep Bering Sea, where benthic nitrate reduction has previously been identified as a significant sink of fixed nitrogen. Porewater profiles from multicores indicate strong 15N enrichment in porewater nitrate at all stations, as one goes deeper in the sediments and nitrate concentrations decrease (δ15N generally reached 25-35‰). Our data are consistent with variable biological isotope effect (ɛ) for dissimilatory nitrate reduction ranging between 13 to 30 ‰. A one-dimensional diffusion-reaction model including organic matter degradation, nitrification, and denitrification indicates that, although denitrification leads to a pore water nitrate pool that is enriched in 15N, N isotope fractionation is poorly expressed at the scale of sediment-water nitrate exchange, independent of whether sediments are a net sink or a net source of nitrate. The apparent nitrate isotope effect of sedimentary denitrification on nitrate in overlying waters is generally below 2‰, as a result of diffusive transport limitation into, and within, the sediments and/or the production of light nitrate during nitrification. Thus, our data suggest that the low expressed isotope effect of benthic denitrification observed previously in reactive shelf sediments also applies to deep-sea sediments. However, where ammonium fluxes out of the sediments, it is enriched in 15-N, and may ultimately lead to an N-isotopic enrichment of the water-column nitrate

  1. Mass-independent isotope effects in planetary atmospheres and the early solar system.

    Science.gov (United States)

    Thiemens, M H

    1999-01-15

    A class of isotope effects that alters isotope ratios on a mass-independent basis provides a tool for studying a wide range of processes in atmospheres of Earth and other planets as well as early processes in the solar nebula. The mechanism for the effect remains uncertain. Mass-independent isotopic compositions have been observed in O3, CO2, N2O, and CO in Earth's atmosphere and in carbonate from a martian meteorite, which suggests a role for mass-independent processes in the atmosphere of Mars. Observed mass-independent meteoritic oxygen and sulfur isotopic compositions may derive from chemical processes in the presolar nebula, and their distributions could provide insight into early solar system evolution.

  2. Sulfur isotope effects associated with protonation of HS- and volatilization of H2S

    Science.gov (United States)

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

    1986-01-01

    The isotope effects associated with: (1) formation of H2S from HS- by protonation in aqueous solution; and (2) volatilization of H2S have been experimentally determined. Both isotopic distributions in closed systems at equilibrium and differential rates of volatilization of isotopic species in open systems were measured at 22 +/- 1 degrees C. It was found that, at equilibrium aqueous H2S is enriched in 34S by 2.0 - 2.7% relative to HS- and that H2S volatilized from solution is depleted in 34S by 0.5% relative to dissolved H2S. A small kinetic isotope effect accompanying volatilization of H2S was observed in the open-system experiments.

  3. Unusual isotope effects of molybdenum in chemical exchange reaction using dicyclohexano-18-crown-6

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Toshiyuki; Nishizawa, Kazushige [Osaka Univ., Suita (Japan). Dept. of Nuclear Engineering; Inagawa, Jun

    1999-06-01

    Molybdenum isotopes were fractionated in a liquid-liquid extraction system using dicyclohexano-18-crown-6 (DC18C6). The enrichment factors showed a breakdown of the conventional mass-dependent rule. Some unusual and larger isotope effects were observed in the even atomic mass isotopes, {sup 92}Mo and {sup 94}Mo. The unusual features in the present study were not responsible for the field shift effect, which was regarded as a primary factor of the anomalous isotope effect in the recent theory, but were due to an anomaly on the vibrational levels. The largest isotope effect was observed in the isotope pair of {sup 94}Mo-{sup 96}Mo, it was {epsilon}{sub 96,94} = 0.0086 {+-} 0.0007, its initial aqueous phase was 0.91 M molybdenum chloride, and its organic phase was 0.2 M DC18C6 in chloroform: this was 0.0043 {+-} 0.0004 in terms of the enrichment factor for unit mass different. (author)

  4. 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

  5. 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.

  6. Oxygen Isotope Evidence for Mn(II)-Catalyzed Recrystallization of Manganite (γ-MnOOH).

    Science.gov (United States)

    Frierdich, Andrew J; Spicuzza, Michael J; Scherer, Michelle M

    2016-06-21

    Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid.

  7. Isotopic evidence for biological nitrogen fixation by molybdenum-nitrogenase from 3.2 Gyr

    Science.gov (United States)

    Stüeken, Eva E.; Buick, Roger; Guy, Bradley M.; Koehler, Matthew C.

    2015-04-01

    Nitrogen is an essential nutrient for all organisms that must have been available since the origin of life. Abiotic processes including hydrothermal reduction, photochemical reactions, or lightning discharge could have converted atmospheric N2 into assimilable NH4+, HCN, or NOx species, collectively termed fixed nitrogen. But these sources may have been small on the early Earth, severely limiting the size of the primordial biosphere. The evolution of the nitrogen-fixing enzyme nitrogenase, which reduces atmospheric N2 to organic NH4+, thus represented a major breakthrough in the radiation of life, but its timing is uncertain. Here we present nitrogen isotope ratios with a mean of 0.0 +/- 1.2‰ from marine and fluvial sedimentary rocks of prehnite-pumpellyite to greenschist metamorphic grade between 3.2 and 2.75 billion years ago. These data cannot readily be explained by abiotic processes and therefore suggest biological nitrogen fixation, most probably using molybdenum-based nitrogenase as opposed to other variants that impart significant negative fractionations. Our data place a minimum age constraint of 3.2 billion years on the origin of biological nitrogen fixation and suggest that molybdenum was bioavailable in the mid-Archaean ocean long before the Great Oxidation Event.

  8. 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.

  9. Direct isotopic evidence for subsistence variability in Middle Pleistocene Neanderthals (Payre, southeastern France)

    Science.gov (United States)

    Bocherens, Hervé; Díaz-Zorita Bonilla, Marta; Daujeard, Camille; Fernandes, Paul; Raynal, Jean-Paul; Moncel, Marie-Hélène

    2016-12-01

    The site of Payre (SE France) is presented as a case study to decipher possible changes in subsistence and land-use strategies during the middle Pleistocene in Europe. This study applies carbon and oxygen isotopic data (δ13C and δ18O) in dental tooth enamel from four distinct Middle Pleistocene Neanderthals coming from two phases of occupation. This allows us to test if these different Neanderthals were similar in their subsistence strategies and mobility during their childhood, and to compare them with terrestrial predators and to herbivores dwelling in different areas around the cave. The results show that Neanderthals were exploiting the environment differently over time in the absence of a significant environmental change. This change of environment exploitation coincides with different durations of occupation. The age of the individuals allows us to discuss the mobility of young Neanderthals and the topographies they lived on before arriving in the cave. The combination of results obtained from various approaches throws a new light on the investigation of Neanderthal ecosystem and land-use patterns during the Early Middle Palaeolithic in Southeastern France.

  10. Iron and Zinc isotope fractionation during magmatism in the continental crust: Evidence from bimodal volcanic rocks from Hailar basin, NE China

    Science.gov (United States)

    Xia, Ying; Li, Shuangqing; Huang, Fang

    2017-09-01

    This study presents Fe-Zn isotope data for a suite of well-characterized bimodal volcanic rocks from Hailar Basin, northeast China to understand the mechanism of Fe isotope fractionation in highly differentiated igneous rocks. The samples range from basaltic trachyandesites to trachytes-rhyodacites, and rhyolites. The δ56Fe values increase with increasing SiO2 contents with the rhyolites having the highest δ56Fe (up to 0.64 ± 0.02‰) among the previously reported data for igneous rocks at a similar SiO2. The lack of correlation between δ56Fe and Rb/La argues against the effect of fluid exsolution on Fe isotopes. The δ56Fe do not show a clear correlation with δ66Zn and radiogenic isotopes, suggesting that thermal diffusion or crustal contamination cannot produce the high δ56Fe in Hailar volcanic rocks. Fe isotopic variation in Hailar volcanic rocks can be explained by two steps of magmatism. During the first step, partial melting of basaltic trachyandesites with an average δ56Fe of 0.09 ± 0.14‰ produced trachytes-rhyodacites with an average δ56Fe of 0.24 ± 0.27‰. Modelling using rhyolite-MELTS shows that Fe isotopes can be fractionated by preferential partitioning of isotopically different Fe3+ and Fe2+ between the solid residue and partial melt. The second step involves formation of rhyolites with significantly high δ56Fe through partial melting or extensive crystallization of crust materials, during which isotopically heavy Fe preferentially partition into the rhyolitic melt. Therefore, fractionation of Fe isotopes between melts and minerals can result in high δ56Fe in SiO2-rich igneous rocks and apparent Fe isotope heterogeneity within the continental crust.

  11. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    Science.gov (United States)

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

    Science.gov (United States)

    Wang, P.; Sun, C.; Ono, S.; Lin, L.

    2012-12-01

    Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates

  13. 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.

  14. 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 (respiration; this was most notable on the Pakistan margin. Depleted foraminiferal δ15N values, particularly at the Oman margin, may reflect feeding on chemosynthetic bacteria. We suggest that differences in productivity regimes may be 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.

  15. Cold seep status archived in authigenic carbonates: Mineralogical and isotopic evidence from Northern South China Sea

    Science.gov (United States)

    Lu, Yang; Sun, Xiaoming; Lin, Zhiyong; Xu, Li; Gong, Junli; Lu, Hongfeng

    2015-12-01

    Cold-seep carbonates are precipitated under high alkalinity conditions created by the anaerobic oxidation of methane in cold-seep sites. Multiple Ca-Mg-carbonate phases are identified, including aragonite, low-Mg calcite (LMC), high-Mg calcite (HMC), protodolomite, and dolomite. These phases result from different conditions that are related with cold-seep activities. Here, we report on the relationship between the Ca-Mg-carbonate phases and the cold-seep status. Authigenic carbonates were sampled from northern slope of South China Sea. Carbon isotopic compositions of samples from Shenhu area are lower than -40‰, indicating methane-derived carbon. The δ13C values of samples from Southwest (SW) Taiwan area range from ~-30‰ to ~-20‰, which is the result of the mixture of methane carbon and seawater carbon. Carbonate phases were identified according to the composition and structure results. Samples from Shenhu area are composed of protodolomite and HMC. Three zones were discovered from the center to the rim of the cross-section of the tube-like sample from SW Taiwan area. From the external to the internal zones, the carbonate phases are HMC; LMC and protodolomite; HMC, respectively. The intensity of superstructure reflections of the protodolomite from Shenhu area is stronger than that from SW Taiwan area, indicating higher MgCO3 content. Based on the formation conditions of Ca-Mg-carbonates from LMC to dolomite, those with higher MgCO3 content are formed in more active cold-seep environment. According to the distribution of carbonate phases in each sample, the cold seep flux was high in Shenhu area and was sustained for a long time. By contrast, the flux in SW Taiwan area was relatively low and not stable. It once became higher, but finally returned to low.

  16. Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

    Science.gov (United States)

    Das, R.; Odom, A. L.

    2007-12-01

    Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1

  17. Equilibrium clumped-isotope effects in doubly substituted isotopologues of ethane

    Science.gov (United States)

    Webb, Michael A.; Wang, Yimin; Braams, Bastiaan J.; Bowman, Joel M.; Miller, Thomas F.

    2017-01-01

    We combine path-integral Monte Carlo methods with a new intramolecular potential energy surface to quantify the equilibrium enrichment of doubly substituted ethane isotopologues due to clumped-isotope effects. Ethane represents the simplest molecule to simultaneously exhibit 13C-13C, 13C-D, and D-D clumped-isotope effects, and the analysis of corresponding signatures may provide useful geochemical and biogeochemical proxies of formation temperatures or reaction pathways. Utilizing path-integral statistical mechanics, we predict equilibrium fractionation factors that fully incorporate nuclear quantum effects, such as anharmonicity and rotational-vibrational coupling which are typically neglected by the widely used Urey model. The magnitude of the calculated fractionation factors for the doubly substituted ethane isotopologues indicates that isotopic clumping can be observed if rare-isotope substitutions are separated by up to three chemical bonds, but the diminishing strength of these effects suggests that enrichment at further separations will be negligible. The Urey model systematically underestimates enrichment due to 13C-D and D-D clumped-isotope effects in ethane, leading to small relative errors in the apparent equilibrium temperature, ranging from 5 K at 273.15 K to 30 K at 873.15 K. We additionally note that the rotameric dependence of isotopologue enrichment must be carefully considered when using the Urey model, whereas the path-integral calculations automatically account for such effects due to configurational sampling. These findings are of direct relevance to future clumped-isotope studies of ethane, as well as studies of 13C-13C, 13C-D, and D-D clumped-isotope effects in other hydrocarbons.

  18. 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.

  19. Coherent phonon decay and the boron isotope effect for MgB2.

    Science.gov (United States)

    Alarco, Jose A; Talbot, Peter C; Mackinnon, Ian D R

    2014-12-14

    Ab initio DFT calculations for the phonon dispersion (PD) and the phonon density of states (PDOS) of the two isotopic forms ((10)B and (11)B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

  20. On the isotope effect in compressed superconducting H3S and D3S

    Science.gov (United States)

    Harshman, Dale R.; Fiory, Anthony T.

    2017-04-01

    A maximum superconductive transition temperature T C = 203.5 K has recently been reported for a sample of the binary compound tri-hydrogen sulfide (H3S) prepared at high pressure and with room temperature annealing. Measurements of T C for H3S and its deuterium counterpart D3S have suggested a mass isotope effect exponent α with anomalous enhancements for reduced applied pressures. While widely cited for evidence of phonon-based superconductivity, the measured T C is shown to exhibit important dependences on the quality and character of the H3S and D3S materials under study; examination of resistance versus temperature data shows that variations in T C and apparent α are strongly correlated with residual resistance ratio, indicative of sensitivity to metallic order. Correlations also extend to the fractional widths of the superconducting transitions. Using resistance data to quantify and compensate for the evident materials differences between H3S and D3S samples, a value of α = 0.043 ± 0.140 is obtained. Thus, when corrected for the varying levels of disorder, the experimental upper limit (≤0.183) lies well below α derived in phonon-based theories.

  1. You are what you eat: Stable isotopic evidence indicates that the naticid gastropod Neverita duplicata is an omnivore

    Directory of Open Access Journals (Sweden)

    Michelle Marie Casey

    2016-11-01

    Full Text Available Species belonging to the family Naticidae (commonly called moon snails are important infaunal gastropod predators found in soft-bottom marine communities worldwide that traditionally have been thought to prey on other mollusks, giving them the expected trophic position of a predator (trophic position = 3. Realized trophic position estimates of the naticid Neverita duplicata from Long Island Sound, however, range between 2.3 and 2.5, indicating omnivory or an anomalously low nitrogen (N fractionation factor. To evaluate the likelihood of omnivory, this study presents whole body stable isotopic analysis of nitrogen and carbon from the soft tissues of laboratory-reared and field-collected N. duplicata. Experimental organisms were maintained on a diet of the bivalve prey Mercenaria mercenaria for one year. The median N fractionation factor derived from the experimental moon snails was 3.58 ‰ thus precluding the presence of an atypical fractionation factor (substantially lower than 3.4 ‰. Numerous molluscan taxa were collected from Long Island Sound in order to evaluate the trophic ecology of N. duplicata in the context of a natural food web. Evidence from the carbon (C signatures of field-collected N. duplicata indicate a reliance on littoral food sources that is inconsistent with a diet of filter-feeding M. mercenaria, even when calculated using the species-specific C fractionation factor derived from the laboratory experiments. Field-collected N. duplicata also show considerable isotopic overlap (N and C with grazing Littorina littorea. For these reasons, we hypothesize that N. duplicata feeds on some combination of benthic primary producers (most likely macroalgae and/or epiphytic diatoms, carrion, and bivalve/gastropod tissue and discuss the ecological implications of potential naticid omnivory.

  2. Impact of deep convection on the isotopic amount effect in tropical precipitation

    Science.gov (United States)

    Tharammal, Thejna; Bala, Govindasamy; Noone, David

    2017-02-01

    The empirical "amount effect" observed in the distribution of stable water isotope ratios in tropical precipitation is used in several studies to reconstruct past precipitation. Recent observations suggest the importance of large-scale organized convection systems on amount effect. With a series of experiments with Community Atmospheric Model version 3.0 with water isotope tracers, we quantify the sensitivity of amount effect to changes in modeled deep convection. The magnitude of the regression slope between long-term monthly precipitation amount and isotope ratios in precipitation over tropical ocean reduces by more than 20% with a reduction in mean deep convective precipitation by about 60%, indicating a decline in fractionation efficiency. Reduced condensation in deep convective updrafts results in enrichment of lower level vapor with heavier isotope that causes enrichment in total precipitation. However, consequent increases in stratiform and shallow convective precipitation partially offset the reduction in the slope of amount effect. The net result is a reduced slope of amount effect in tropical regions except the tropical western Pacific, where the effects of enhanced large-scale ascent and increased stratiform precipitation prevail over the influence of reduced deep convection. We also find that the isotope ratios in precipitation are improved over certain regions in the tropics with reduced deep convection, showing that analyses of isotope ratios in precipitation and water vapor are powerful tools to improve precipitation processes in convective parameterization schemes in climate models. Further, our study suggests that the precipitation types over a region can alter the fractionation efficiency of isotopes with implications for the reconstructions of past precipitation.

  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.

  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. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  6. 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

  7. Unglaciated areas in East Antarctica during the Last Glacial (Marine Isotope Stage 3) - New evidence from Rauer Group

    Science.gov (United States)

    Berg, Sonja; White, Duanne A.; Bennike, Ole; Fülöp, Réka-H.; Fink, David; Wagner, Bernd; Melles, Martin

    2016-12-01

    Limited information on the East Antarctic Ice Sheet (EAIS) geometry during Marine Isotope Stage 3 (MIS 3; 60-25 ka) restricts our understanding of its behaviour during periods of climate and sea level change. Ice sheet models forced by global parameters suggest an expanded EAIS compared to the Holocene during MIS 3, but field evidence from East Antarctic coastal areas contradicts such modelling, and suggests that the ice sheet margins were no more advanced than at present. Here we present a new lake sediment record, and cosmogenic exposure results from bedrock, which confirm that Rauer Group (eastern Prydz Bay) was ice-free for much of MIS 3. We also refine the likely duration of the Last Glacial Maximum (LGM) glaciation in the region. Lacustrine and marine sediments from Rauer Group indicate the penultimate period of ice retreat predates 50 ka. The lacustrine record indicates a change from warmer/wetter conditions to cooler/drier conditions after ca. 35 ka. Substantive ice sheet re-advance, however, may not have occurred until much closer to 20 ka. Contemporary coastal areas were still connected to the sea during MIS 3, restricting the possible extent of grounded ice in Prydz Bay on the continental shelf. In contrast, relative sea levels (RSL) deduced from field evidence indicate an extra ice load averaging several hundred metres thicker ice across the Bay between 45 and 32 ka. Thus, ice must either have been thicker immediately inland (with a steeper ice profile), or there were additional ice domes on the shallow banks of the outer continental shelf. Further work is required to reconcile the differences between empirical evidence of past ice sheet histories, and the history predicted by ice sheet models from far-field temperature and sea level records.

  8. Kinetic and metabolic isotope effects in coral skeletal carbon isotopes: A re-evaluation using experimental coral bleaching as a case study

    Science.gov (United States)

    Schoepf, Verena; Levas, Stephen J.; Rodrigues, Lisa J.; McBride, Michael O.; Aschaffenburg, Matthew D.; Matsui, Yohei; Warner, Mark E.; Hughes, Adam D.; Grottoli, Andréa G.

    2014-12-01

    Coral skeletal δ13C can be a paleo-climate proxy for light levels (i.e., cloud cover and seasonality) and for photosynthesis to respiration (P/R) ratios. The usefulness of coral δ13C as a proxy depends on metabolic isotope effects (related to changes in photosynthesis) being the dominant influence on skeletal δ13C. However, it is also influenced by kinetic isotope effects (related to calcification rate) which can overpower metabolic isotope effects and thus compromise the use of coral skeletal δ13C as a proxy. Heikoop et al. (2000) proposed a simple data correction to remove kinetic isotope effects from coral skeletal δ13C, as well as an equation to calculate P/R ratios from coral isotopes. However, despite having been used by other researchers, the data correction has never been directly tested, and isotope-based P/R ratios have never been compared to P/R ratios measured using respirometry. Experimental coral bleaching represents a unique environmental scenario to test this because bleaching produces large physiological responses that influence both metabolic and kinetic isotope effects in corals. Here, we tested the δ13C correction and the P/R calculation using three Pacific and three Caribbean coral species from controlled temperature-induced bleaching experiments where both the stable isotopes and the physiological variables that cause isotopic fractionation (i.e., photosynthesis, respiration, and calcification) were simultaneously measured. We show for the first time that the data correction proposed by Heikoop et al. (2000) does not effectively remove kinetic effects in the coral species studied here, and did not improve the metabolic signal of bleached and non-bleached corals. In addition, isotope-based P/R ratios were in poor agreement with measured P/R ratios, even when the data correction was applied. This suggests that additional factors influence δ13C and δ18O, which are not accounted for by the data correction. We therefore recommend that the

  9. The stable isotope amount effect: New insights from NEXRAD echo tops, Luquillo Mountains, Puerto Rico

    Science.gov (United States)

    Schol, M.A.; Shanley, J.B.; Zegarra, J.P.; Coplen, T.B.

    2009-01-01

    The stable isotope amount effect has often been invoked to explain patterns of isotopic composition of rainfall in the tropics. This paper describes a new approach, correlating the isotopic composition of precipitation with cloud height and atmospheric temperature using NEXRAD radar echo tops, which are a measure of the maximum altitude of rainfall within the clouds. The seasonal differences in echo top altitudes and their corresponding temperatures are correlated with the isotopic composition of rainfall. These results offer another factor to consider in interpretation of the seasonal variation in isotopic composition of tropical rainfall, which has previously been linked to amount or rainout effects and not to temperature effects. Rain and cloud water isotope collectors in the Luquillo Mountains in northeastern Puerto Rico were sampled monthly for three years and precipitation was analyzed for ??18O and ??2H. Precipitation enriched in , 18O and 2H occurred during the winter dry season (approximately December-May) and was associated with a weather pattern of trade wind showers and frontal systems. During the summer rainy season (approximately June-November), precipitation was depleted in 18O and 2H and originated in low pressure systems and convection associated with waves embedded in the prevailing easterly airflow. Rain substantially depleted in 18O and 2H compared to the aforementioned weather patterns occurred during large low pressure systems. Weather analysis showed that 29% of rain input to the Luquillo Mountains was trade wind orographic rainfall, and 30% of rainfall could be attributed to easterly waves and low pressure systems. Isotopic signatures associated with these major climate patterns can be used to determine their influence on streamflow and groundwater recharge and to monitor possible effects of climate change on regional water resources.

  10. Variation in oxygen isotope fractionation during cellulose synthesis: intramolecular and biosynthetic effects.

    Science.gov (United States)

    Sternberg, Leonel; Pinzon, Maria Camila; Anderson, William T; Jahren, A Hope

    2006-10-01

    The oxygen isotopic composition of plant cellulose is commonly used for the interpretations of climate, ecophysiology and dendrochronology in both modern and palaeoenvironments. Further applications of this analytical tool depends on our in-depth knowledge of the isotopic fractionations associated with the biochemical pathways leading to cellulose. Here, we test two important assumptions regarding isotopic effects resulting from the location of oxygen in the carbohydrate moiety and the biosynthetic pathway towards cellulose synthesis. We show that the oxygen isotopic fractionation of the oxygen attached to carbon 2 of the glucose moieties differs from the average fractionation of the oxygens attached to carbons 3-6 from cellulose by at least 9%, for cellulose synthesized within seedlings of two different species (Triticum aestivum L. and Ricinus communis L.). The fractionation for a given oxygen in cellulose synthesized by the Triticum seedlings, which have starch as their primary carbon source, is different than the corresponding fractionation in Ricinus seedlings, within which lipids are the primary carbon source. This observation shows that the biosynthetic pathway towards cellulose affects oxygen isotope partitioning, a fact heretofore undemonstrated. Our findings may explain the species-dependent variability in the overall oxygen isotope fractionation during cellulose synthesis, and may provide much-needed insight for palaeoclimate reconstruction using fossil cellulose.

  11. Soil carbon dioxide emissions from the Mojave desert: Isotopic evidence for a carbonate source

    Science.gov (United States)

    Soper, Fiona M.; McCalley, Carmody K.; Sparks, Kimberlee; Sparks, Jed P.

    2017-01-01

    Arid soils represent a substantial carbonate pool and may participate in surface-atmosphere CO2 exchange via a diel cycle of carbonate dissolution and exsolution. We used a Keeling plot approach to determine the substrate δ13C of CO2 emitted from carbonate-dominated soils in the Mojave desert and found evidence for a nonrespiratory source that increased with surface temperature. In dry soils at 25-30°C, the CO2 substrate had δ13C values of -19.4 ± 4.2‰, indicative of respiration of organic material (soil organic matter = -23.1 ± 0.8‰). CO2 flux increased with temperature; maximum fluxes occurred above 60°C, where δ13CO2 substrate (-7.2‰ ± 2.8‰) approached soil carbonate values (0.2 ± 0.2‰). In wet soils, CO2 emissions were not temperature dependent, and δ13CO2 substrate was lower in vegetated soils with higher flux rates, higher organic C content, and potential root respiration. These data provide the first direct evidence of CO2 emissions from alkaline desert soils derived from an abiotic source and that diurnal emission patterns are strongly driven by surface temperature.

  12. Stable isotopic (O, H) evidence for hydration of the central Colorado Plateau lithospheric mantle by slab-derived fluids

    Science.gov (United States)

    Marshall, E. W.; Barnes, J.; Lassiter, J. C.

    2013-12-01

    The Colorado Plateau is a tectonically stable, relatively undeformed Proterozoic lithospheric province in the North America Cordillera. Although the stability of the Colorado Plateau suggests that it is rheologically strong, evidence from xenoliths show that the lithospheric mantle is extensively hydrated (e.g., presence of hydrous minerals, 'high' water contents in nominally anhydrous minerals), and therefore weakened. In addition, LREE enrichments in clinopyroxene (cpx) imply that the lithospheric mantle has been metasomatized ([1],[2]). Here we analyze mineral separates from spinel and garnet peridotite xenoliths from the Navajo Volcanic Field (NVF), located in the center of the Plateau, for their oxygen and hydrogen isotope compositions. These compositions are compared to those of xenoliths at the margins of the Plateau: spinel peridotites from the Grand Canyon Volcanic Field (GCVF) in the west and Zuni-Bandera Volcanic Field (ZBVF) in the east. NVF xenoliths are significantly more hydrous than the xenoliths on the margins of the Colorado Plateau based on modal abundances of hydrous minerals and structural water in olivine (e.g. [3]). All hydrous phases have high δD values (antigorite = -71 to -46‰ (n = 6 xenoliths); chlorite = -49 to -31‰ (n=3); amphibole = -47‰ (n=1)) compared to normal mantle (~-80‰), suggesting the addition of a fluid that is enriched in D compared to typical mantle. δ18O values for the same hydrous minerals range from 6.0 to 6.6‰ (n=6). δ18O values of olivine from NVF spinel peridotites have a narrow range, 5.0 to 5.4‰ (n = 4), near mantle olivine values (~5.2‰). Olivines from spinel peridotites from the GCVF and ZBVF also have mantle-like δ18O values (5.1 to 5.2‰ (n=3) and 5.1 to 5.4‰ (n=7), respectively). However, olivines and orthopyroxenes (opx) from NVF garnet peridotites have a slightly larger range and some record 18O enrichment (olivine = 5.1 to 5.6‰ (n = 3); opx = 5.9‰ (n=1)). The high δ18O values of

  13. 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 method enables the determination of both the electronic and the protonic (deuteronic) wave functions simultaneously and can directly calculate the geometrical difference induced by H/D isotope effects. The calculations show that the one-bond deuterium isotope effects on 15N nuclear shielding, 1Δ15N......(D), in ammonium and amines decrease as a counterion or water molecule moves closer to the nitrogen. 1Δ15N(D) and 2Δ1H(D) of the NH3+ groups of lysine residues in the B1 domain of protein G have been calculated using truncated side chains and also determined experimentally by NMR. Comparisons show...

  14. 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 (<20%) and variable amounts of a basalt or komatiite component. This component was added as either subducted oceanic crust or melt derived from greater depths in the mantle. These results suggest that the Re - Os isotope system may be a highly sensitive indicator of the presence of ancient subducted oceanic crust in mantle-source regions. ?? 1991 Springer-Verlag.

  15. 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

    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......” 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...

  16. Influence of Isotope on Shell Effects of Pre-scission Particle Evaporation

    Institute of Scientific and Technical Information of China (English)

    YE Wei; CHEN Na

    2005-01-01

    The shell effects on the particle evaporation prior to fission for three Pb isotopes, 204pb, 20sPb, and 212pb,as well as three Sn isotopes, 128Sn, 132Sn, and 136Sn, are explored by a diffusion model. Calculations show that the magnitude of shell effects in the emission of particles changes with the neutron-to-proton ratio N/Z of these fissioning nuclei, and this change is affected significantly by the spin and excitation energy of the system. It is shown that high angular momentum enhances the dependence of shell effects on the N/Z while high excitation energy weakens such a dependence.

  17. Soil organic carbon dynamics under long-term fertilization in a black soil of China: Evidence from stable C isotopes

    Science.gov (United States)

    Dou, Xiaolin; He, Ping; Zhu, Ping; Zhou, Wei

    2016-01-01

    Effects of different fertilizers on organic carbon (C) storage and turnover of soil fractions remains unclear. We combined soil fractionation with isotope analyses to examine soil organic carbon (SOC) dynamics after 25 years of fertilization. Five types of soil samples including the initial level (CK) and four fertilization treatments (inorganic nitrogen fertilizer, N; balanced inorganic fertilizer, NPK; inorganic fertilizer plus farmyard manure, MNPK; inorganic fertilizer plus corn straw residue, SNPK) were separated into four aggregate sizes (>2000 μm, 2000–250 μm, 250–53 μm, and 250 μm aggregates but reduced SOC storage in <250 μm aggregates due to SOC changes in LF and iPOM. PMID:26898121

  18. 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.

  19. Enantiomer signature and carbon isotope evidence for the migration and transformation of DDTs in arable soils across China

    Science.gov (United States)

    Niu, Lili; Xu, Chao; Zhu, Siyu; Bao, Huiming; Xu, Yang; Li, Hongyi; Zhang, Zhijian; Zhang, Xichang; Qiu, Jiguo; Liu, Weiping

    2016-12-01

    Due to the adverse impact of DDTs on ecosystems and humans, a full fate assessment deems a comprehensive study on their occurrence in soils over a large region. Through a sampling campaign across China, we measured the concentrations, enantiomeric fractions (EFs), compound-specific carbon isotope composition of DDT and its metabolites, and the microbial community in related arable soils. The geographically total DDT concentrations are higher in eastern than western China. The EFs and δ13C of o,p’-DDT in soils from western China show smaller deviations from those of racemic/standard compound, indicating the DDT residues there mainly result from atmospheric transport. However, the sources of DDT in eastern China are mainly from historic application of technical DDTs and dicofol. The inverse dependence of o,p’-DDT and p,p’-DDE on temperature evidences the transformation of parent DDT to its metabolites. Initial usage, abiotic parameters and microbial communities are found to be the main factors influencing the migration and transformation of DDT isomers and their metabolites in soils. In addition, a prediction equation of DDT concentrations in soils based on stepwise multiple regression analysis is developed. Results from this study offer insights into the migration and transformation pathways of DDTs in Chinese arable soils, which will allow data-based risk assessment on their use.

  20. Stable carbon isotope evidence for tracing the diet of the host Hepialus larva of Cordyceps sinensis in the Tibetan Plateau

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Two types of Hepialus larvae with different diets were distinguished in the Sejila Mountain,Tibetan Plateau based on the stable carbon isotope data of the host Hepialus larva of Cordyceps sinensis and its closely adjacent tender plant roots and humus fractions.Type I is the larva chiefly fed by soil humus,and characterized by the δ 13C values of -22.6‰ to-23.4‰,and more than -23.4‰ in its heads.Type II is the larva chiefly fed by tender plant roots,and characterized by the δ 13C values of-24.6‰ to -27.6‰,and less than -24.6‰ in its heads.Our result has exceeded the traditional understanding that their food sources only come from the tender plant roots,and may provide evidence for choosing cheap and high-quality foods and further establishing artificial habitats in their large-scale reproduction.

  1. Heterogeneous Isotopic Anomalies of Sm and Gd in the Norton County Meteorite: Evidence for Irradiation from the Active Early Sun

    Science.gov (United States)

    Hidaka, Hiroshi; Kondo, Tomoyo; Yoneda, Shigekazu

    2012-02-01

    Large and heterogeneous isotopic variations of 150Sm/149Sm and 158Gd/157Gd due to neutron capture reactions caused by cosmic-ray irradiation were found in chemical and mineral separates from the Norton County meteorite. The light-colored separates, consisting mainly of enstatite (Mg2Si2O6), have a very large neutron fluence of 1.98 × 1017 n cm-2, which is 10 times higher than that of the whole rock. Furthermore, four chemical separates showed a large variation in neutron fluences, ranging from 1.82 × 1016 to 1.87 × 1017 n cm-2. The variable amounts of neutron fluences from a small single fragment of the Norton County meteorite cannot be simply explained by single-stage cosmic-ray irradiation in space. Rare earth element (REE) analyses revealed that the fractions with high neutron fluences have similar chemical properties to those in the early condensates in the solar system, showing depletions of Eu and Yb in their REE abundance patterns. The data provide evidence for an activity of the early Sun (T Tauri), suggesting the migration of early and intense irradiation materials into the Norton County meteorite's parent body.

  2. VAPOR PRESSURE ISOTOPE EFFECTS IN THE MEASUREMENT OF ENVIRONMENTAL TRITIUM SAMPLES.

    Energy Technology Data Exchange (ETDEWEB)

    Kuhne, W.

    2012-12-03

    Standard procedures for the measurement of tritium in water samples often require distillation of an appropriate sample aliquot. This distillation process may result in a fractionation of tritiated water and regular light water due to the vapor pressure isotope effect, introducing either a bias or an additional contribution to the total tritium measurement uncertainty. The magnitude of the vapor pressure isotope effect is characterized as functions of the amount of water distilled from the sample aliquot and the heat settings for the distillation process. The tritium concentration in the distillate is higher than the tritium concentration in the sample early in the distillation process, it then sharply decreases due to the vapor pressure isotope effect and becomes lower than the tritium concentration in the sample, until the high tritium concentration retained in the boiling flask is evaporated at the end of the process. At that time, the tritium concentration in the distillate again overestimates the sample tritium concentration. The vapor pressure isotope effect is more pronounced the slower the evaporation and distillation process is conducted; a lower heat setting during the evaporation of the sample results in a larger bias in the tritium measurement. The experimental setup used and the fact that the current study allowed for an investigation of the relative change in vapor pressure isotope effect in the course of the distillation process distinguish it from and extend previously published measurements. The separation factor as a quantitative measure of the vapor pressure isotope effect is found to assume values of 1.034 {+-} 0.033, 1.052 {+-} 0.025, and 1.066 {+-} 0.037, depending on the vigor of the boiling process during distillation of the sample. A lower heat setting in the experimental setup, and therefore a less vigorous boiling process, results in a larger value for the separation factor. For a tritium measurement in water samples, this implies that

  3. Comparisons of phosphorothioate with phosphate transfer reactions for a monoester, diester, and triester: isotope effect studies.

    Science.gov (United States)

    Catrina, Irina E; Hengge, Alvan C

    2003-06-25

    Phosphorothioate esters are sometimes used as surrogates for phosphate ester substrates in studies of enzymatic phosphoryl transfer reactions. To gain better understanding of the comparative inherent chemistry of the two types of esters, we have measured equilibrium and kinetic isotope effects for several phosphorothioate esters of p-nitrophenol (pNPPT) and compared the results with data from phosphate esters. The primary (18)O isotope effect at the phenolic group ((18)k(bridge)), the secondary nitrogen-15 isotope effect ((15)k) in the nitro group, and (for the monoester and diester) the secondary oxygen-18 isotope effect ((18)k(nonbridge)) in the phosphoryl oxygens were measured. The equilibrium isotope effect (EIE) (18)k(nonbridge) for the deprotonation of the monoanion of pNPPT is 1.015 +/- 0.002, very similar to values previously reported for phosphate monoesters. The EIEs for complexation of Zn(2+) and Cd(2+) with the dianion pNPPT(2-) were both unity. The mechanism of the aqueous hydrolysis of the monoanion and dianion of pNPPT, the diester ethyl pNPPT, and the triester dimethyl pNPPT was probed using heavy atom kinetic isotope effects. The results were compared with the data reported for analogous phosphate monoester, diester, and triester reactions. The results suggest that leaving group bond fission in the transition state of reactions of the monoester pNPPT is more advanced than for its phosphate counterpart pNPP, while alkaline hydrolysis of the phosphorothioate diester and triester exhibits somewhat less advanced bond fission than that of their phosphate ester counterparts.

  4. The two Suvasvesi impact structures, Finland: Argon isotopic evidence for a "false" impact crater doublet

    Science.gov (United States)

    Schmieder, Martin; Schwarz, Winfried H.; Trieloff, Mario; Buchner, Elmar; Hopp, Jens; Tohver, Eric; Pesonen, Lauri J.; Lehtinen, Martti; Moilanen, Jarmo; Werner, Stephanie C.; Öhman, Teemu

    2016-05-01

    The two neighboring Suvasvesi North and South impact structures in central-east Finland have been discussed as a possible impact crater doublet produced by the impact of a binary asteroid. This study presents 40Ar/39Ar geochronologic data for impact melt rocks recovered from the drilling into the center of the Suvasvesi North impact structure and melt rock from glacially transported boulders linked to Suvasvesi South. 40Ar/39Ar step-heating analysis yielded two essentially flat age spectra indicating a Late Cretaceous age of ~85 Ma for the Suvasvesi North melt rock, whereas the Suvasvesi South melt sample gave a Neoproterozoic minimum (alteration) age of ~710 Ma. Although the statistical likelihood for two independent meteorite strikes in close proximity to each other is rather low, the remarkable difference in 40Ar/39Ar ages of >600 Myr for the two Suvasvesi impact melt samples is interpreted as evidence for two temporally separate, but geographically closely spaced, impacts into the Fennoscandian Shield. The Suvasvesi North and South impact structures are, thus, interpreted as a "false" crater doublet, similar to the larger East and West Clearwater Lake impact structures in Québec, Canada, recently shown to be unrelated. Our findings have implications for the reliable recognition of impact crater doublets and the apparent rate of binary asteroid impacts on Earth and other planetary bodies in the inner solar system.

  5. Chemical and isotopic evidence for the in situ origin of marine humic substances

    Energy Technology Data Exchange (ETDEWEB)

    Nissenbaum, A.; (Weizmann Inst., Rehovot, Israel); Kaplan, I.R.

    1972-07-01

    Humic and fulvic acids were extracted from marine and nonmarine Recent sediments and from soils. These acids are shown to be major components of the organic matter from marine and nonmarine sediments--some marine sediments may contain 70% of their organic carbon in the humic and fulvic acid fraction. Marine and terrestrial humic acids have similar carbon and hydrogen content, but the former generally contain more sulfur and nitrogen. delta/sup 34/S values of marine humic acid indicate that the sulfur is introduced into the organic matter as hydrogen sulfide produced by sulfate reduction. Marine humates have a rather constant delta/sup 13/C value of -20 to -22%, whereas the delta/sup 13/C of soil humic acid is related to its plant source material and usually ranges around -25 to -26%. The evidence shows that marine humic acids can be formed in situ from degradation products of plankton and are not necessarily transported from the continent. The suggested pathway of marine humic acid formation and transformation in the sediment is (1) degraded cellular material..-->..(2) water-soluble complex containing amino acids and carbohydrates..-->..(3) fulvic acids..-->..(4) humic acids..-->..(5) kerogen.

  6. Evidence for the Mechanism Behind the Biasing of Organic Matter's Isotopic Carbon Signal during Pre-preparation Removal of Inorganic Carbonate

    Science.gov (United States)

    Casford, J. S.; Brodie, C.; Casford, M. T.

    2012-12-01

    We investigate the potential mechanisms behind the known and significant biasing of the organic matter carbon (and nitrogen) isotopic signal during the pre-preparation removal of inorganic carbonates. This effect was quantified by Brodie et al (2012 Chemical Geology) and shown to be both significant and non-linear. Using a combination of IR-spectroscopy, 13C NMR and GC-MS, we compare before and after treatment samples of 2 known standards (an total organic plant sample BROC and a soil standard -SOILB) and one 'real' sediment core sample (from a Lake in southern China - TYC). These were subjected to the most commonly used pre-preparation acidification, using differing concentrations of HCL, to provide a first look at the potential mechanisms behind this bias. Provisional results suggest at least 3 factors in play during the pre-preparation; 1. The loss of n-alkanes compounds because of the acidification. 2. A potential increase in the proportion of Carbonyl groups 3. And an increase in clay mineral hydration (in TYC and possibly in Soil B). We also note a potential change in particle size distribution after treatment that may also effect the hominization of the samples. This provide the first clear evidence for the nature of the widely observed but poorly understood biasing effect

  7. Oxygen Isotopes in Meteorites

    Science.gov (United States)

    Clayton, R. N.

    2003-12-01

    Oxygen isotope abundance variations in meteorites are very useful in elucidating chemical and physical processes that occurred during the formation of the solar system (Clayton, 1993). On Earth, the mean abundances of the three stable isotopes are 16O: 99.76%, 17O: 0.039%, and 18O: 0.202%. It is conventional to express variations in abundances of the isotopes in terms of isotopic ratios, relative to an arbitrary standard, called SMOW (for standard mean ocean water), as follows:The isotopic composition of any sample can then be represented by one point on a "three-isotope plot," a graph of δ17O versus δ18O. It will be seen that such plots are invaluable in interpreting meteoritic data. Figure 1 shows schematically the effect of various processes on an initial composition at the center of the diagram. Almost all terrestrial materials lie along a "fractionation" trend; most meteoritic materials lie near a line of "16O addition" (or subtraction). (4K)Figure 1. Schematic representation of various isotopic processes shown on an oxygen three-isotope plot. Almost all terrestrial materials plot along a line of "fractionation"; most primitive meteoritic materials plot near a line of "16O addition." The three isotopes of oxygen are produced by nucleosynthesis in stars, but by different nuclear processes in different stellar environments. The principal isotope, 16O, is a primary isotope (capable of being produced from hydrogen and helium alone), formed in massive stars (>10 solar masses), and ejected by supernova explosions. The two rare isotopes are secondary nuclei (produced in stars from nuclei formed in an earlier generation of stars), with 17O coming primarily from low- and intermediate-mass stars (shielding in the UV photodissociation of CO (van Dishoeck and Black, 1988). This process results from the large differences in abundance between C16O, on the one hand, and C17O and C18O on the other. Photolysis of CO occurs by absorption of stellar UV radiation in the

  8. Sulfur isotope composition of metasomatised mantle xenoliths from the Bultfontein kimberlite (Kimberley, South Africa): Contribution from subducted sediments and the effect of sulfide alteration on S isotope systematics

    Science.gov (United States)

    Giuliani, Andrea; Fiorentini, Marco L.; Martin, Laure A. J.; Farquhar, James; Phillips, David; Griffin, William L.; LaFlamme, Crystal

    2016-07-01

    Sulfur isotopes are a powerful geochemical tracer in high-temperature processes, but have rarely been applied to the study of mantle metasomatism. In addition, there are very limited S isotope data on sub-continental lithospheric mantle (SCLM) material. For cratonic regions, these data are restricted to sulfide inclusions in diamonds. To provide new constraints on the S isotope composition of the SCLM and on the source(s) of mantle metasomatic fluids beneath the diamondiferous Kimberley region (South Africa), we investigated the S isotope systematics of five metasomatised mantle xenoliths from the Bultfontein kimberlite. Pentlandite and chalcopyrite in these xenoliths were analysed by in situ secondary-ion mass spectrometry (SIMS), with bulk-rock material measured by gas source isotope ratio mass spectrometry techniques. Based on previous studies, the xenoliths experienced different types of metasomatism to one another at distinct times (∼180 and ∼90-80 Ma). Contained pentlandite grains show variable alteration to heazlewoodite (i.e. Ni sulfide) + magnetite. The in situ S isotope analyses of pentlandite exhibit a relatively restricted range between -5.9 and - 1.4 ‰δ34 S (compared to VCDT), with no statistically meaningful differences between samples. Chalcopyrite only occurs in one sample and shows δ34 S values between -5.4 and - 1.0 ‰. The bulk-rock Ssulfide isotope analyses vary between -3.4 and + 0.8 ‰δ34 S. Importantly, the only sample hosting dominantly fresh sulfides shows a bulk-rock δ34 S value consistent with the mean value for the sulfides, whereas the other samples exhibit higher bulk 34S/32S ratios. The differences between bulk-rock and average in situδ34 S values are directly correlated with the degree of sulfide alteration. This evidence indicates that the elevated 34S/32S ratios in the bulk samples are not due to the introduction of heavy S (commonly as sulfates) and are best explained by isotopic fractionation coupled with the removal

  9. Isotope Effect on Electron-Phonon Coupling in Multiband Superconductor MgB2

    Science.gov (United States)

    Mou, Daixiang; Taufour, Valentin; Wu, Yun; Huang, Lunan; Bud'Ko, Serguei; Canfield, Paul; Kaminski, Adam

    We systematically investigate the isotope effect of electron-phonon coupling in multi-band superconductor MgB2 by laser based Angle Resolved Photoemission Spectroscopy. The kink structure around 70 meV on two σ bands, which is caused by electron coupling to E2 g phonon mode, is shifted to higher binding energy in Mg10B2 than that in Mg11B2. The measured shifting energy of 3.5 meV is consistent with theoretical calculation based on harmonic phonon in MgB2. Our temperature dependent measurement also indicates the isotope effect of kink structure is not dependent on superconducting transition.

  10. Isotope effect on electron-phonon interaction in the multiband superconductor MgB2

    Science.gov (United States)

    Mou, Daixiang; Manni, Soham; Taufour, Valentin; Wu, Yun; Huang, Lunan; Bud'ko, S. L.; Canfield, P. C.; Kaminski, Adam

    2016-04-01

    We investigate the effect of isotope substitution on the electron-phonon interaction in the multiband superconductor MgB2 using tunable laser-based angle-resolved photoemission spectroscopy. The kink structure around 70 meV in the σ band, which is caused by electron coupling to the E2 g phonon mode, is shifted to higher binding energy by ˜3.5 meV in Mg 10B2 and the shift is not affected by superconducting transition. These results serve as the benchmark for investigations of isotope effects in known, unconventional superconductors and newly discovered superconductors where the origin of pairing is unknown.

  11. Oxygen isotope effect in cuprates results from polaron-induced superconductivity

    OpenAIRE

    Weyeneth, S.; Müller, K. A.

    2011-01-01

    The planar oxygen isotope effect coefficient measured as a function of hole doping in the Pr- and La-doped YBa2Cu3O7 (YBCO) and the Ni-doped La1.85Sr0.15CuO4 (LSCO) superconductors quantitatively and qualitatively follows the form originally proposed by Kresin and Wolf [Phys. Rev. B 49, 3652 (1994)], which was derived for polarons perpendicular to the superconducting planes. Interestingly, the inverse oxygen isotope effect coefficient at the pseudogap temperature also obeys the...

  12. The influence of anharmonic phonons on the isotope effect in high-{Tc} oxides

    Energy Technology Data Exchange (ETDEWEB)

    Crespi, V.H.; Cohen, M.L.

    1992-01-01

    Anharmonic phonons are examined to study the unusual isotope effect exponents for the high-{Tc} oxides. Within a simple model of anharmonicity, the mass dependences of the electron-phonon coupling constant {lambda} and the phonon frequency determine the isotope effect exponent {alpha} as a function of coupling strength. A model in which the outer wells of a multiple-well potential deepen as the orthorhombic/low temperature tetragonal phase transition in La{sub 2-x}M{sub x}CuO{sub 4} is approached is consistent with some experimentally observed variations in {Tc} and {alpha}. 10 refs.

  13. The influence of anharmonic phonons on the isotope effect in high- Tc oxides

    Energy Technology Data Exchange (ETDEWEB)

    Crespi, V.H.; Cohen, M.L.

    1992-01-01

    Anharmonic phonons are examined to study the unusual isotope effect exponents for the high-{Tc} oxides. Within a simple model of anharmonicity, the mass dependences of the electron-phonon coupling constant {lambda} and the phonon frequency determine the isotope effect exponent {alpha} as a function of coupling strength. A model in which the outer wells of a multiple-well potential deepen as the orthorhombic/low temperature tetragonal phase transition in La{sub 2-x}M{sub x}CuO{sub 4} is approached is consistent with some experimentally observed variations in {Tc} and {alpha}. 10 refs.

  14. The effect of small scale variablity in isotopic composition of precipitation on hydrograph separation results

    Science.gov (United States)

    Fischer, Benjamin; van Meerveld, Ilja; Seibert, Jan

    2016-04-01

    Understanding runoff processes is important for predictions of streamflow quantity and quality. The two-component isotope hydrograph separation (IHS) method is a valuable tool to study how catchments transform rainfall into runoff. IHS allows the stormflow hydrograph to be separated into rainfall (event water) and water that was stored in the catchment before the event (pre-event water). To be able to perform an IHS, water samples of baseflow (pre-event water) and stormflow are collected at the stream outlet. Rainfall is usually collected at one location by hand as an event total or sampled sequentially during the event. It is usually assumed that the spatial variability in rainfall and the isotopic composition of rainfall are negligible for small (area of 0.15, 0.23, and 0.7 km2). The isotopic composition of rainfall and streamflow were sampled for 10 different rain events (P: 5 mm intervals, Q: 12 to 51 samples per events). This dataset was used to perform a two-component isotope hydrograph separation. The results show that for some events the spatial variability in total rainfall, mean and maximum rainfall intensity and stable isotope composition of rainfall was high. There was no relation between the stable isotope composition of rainfall and the rainfall sum, rainfall intensity or altitude. The spatial variability of the isotopic composition of rainfall was for 4 out of the 10 events as large as the temporal variability in the isotopic composition. Different rainfall weighing methods resulted in different minimum pre-event water fractions in streamflow. For small events with a small mean temporal range in stable isotope composition of rainfall, the different rainfall weighing methods had little effect on the calculated minimum pre-event water fractions. However with increasing temporal variability in stable isotope composition of rainfall, the range in the minimum pre-event water fractions increased and therefore the choice of the rainfall weighing method

  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. Anharmonicity effects in impurity-vacancy centers in diamond revealed by isotopic shifts and optical measurements

    Science.gov (United States)

    Ekimov, E. A.; Krivobok, V. S.; Lyapin, S. G.; Sherin, P. S.; Gavva, V. A.; Kondrin, M. V.

    2017-03-01

    We studied isotopically enriched nano- and microdiamonds with optically active GeV- centers synthesized at high pressures and high temperatures in nonmetallic growth systems. The influence of isotopic composition on optical properties has been thoroughly investigated by photoluminescence-excitation (PLE) and photoluminescence (PL) spectroscopy to get insight into the nature and electronic structure of this color center. We have demonstrated that the large frequency defect (difference between oscillation frequencies in the ground and excited electronic states) does bring about large discrepancy between PLE and PL spectra and comparatively high isotopic shift of the zero phonon line. Both effects seem to be rather common to split-vacancy centers (for example SiV-), where the frequency defect reaches record high values. Isotopic substitution of carbon atoms in the diamond lattice results in even larger shifts, which are only partially accounted for by a redistribution of electron density caused by the volume change of the diamond lattice. It was shown that the vibronic frequency in this case does not depend on the mass of carbon atoms. The greatest part of this isotopic shift is due to anharmonicity effects, which constitute a substantial part of vibronic frequency observed in this center. The exact physical mechanism, which leads to significant enhancement of anharmonicity on substitution of 12C to 13C, is yet to be clarified.

  17. Source of boron in the Palokas gold deposit, northern Finland: evidence from boron isotopes and major element composition of tourmaline

    Science.gov (United States)

    Ranta, Jukka-Pekka; Hanski, Eero; Cook, Nick; Lahaye, Yann

    2016-11-01

    The recently discovered Palokas gold deposit is part of the larger Rompas-Rajapalot gold-mineralized system located in the Paleoproterozoic Peräpohja Belt, northern Finland. Tourmaline is an important gangue mineral in the Palokas gold mineralization. It occurs as tourmalinite veins and as tourmaline crystals in sulfide-rich metasomatized gold-bearing rocks. In order to understand the origin of tourmaline in the gold-mineralized rocks, we have investigated the major element chemistry and boron isotope composition of tourmaline from three areas: (1) the Palokas gold mineralization, (2) a pegmatitic tourmaline granite, and (3) the evaporitic Petäjäskoski Formation. Based on textural evidence, tourmaline in gold mineralization is divided into two different types. Type 1 is located within the host rock and is cut by rock-forming anthophyllite crystals. Type 2 occurs in late veins and/or breccia zones consisting of approximately 80% tourmaline and 20% sulfides, commonly adjacent to quartz veins. All the studied tourmaline samples belong to the alkali-group tourmaline and can be classified as dravite and schorl. The δ11B values of the three localities lie in the same range, from 0 to -4‰. Tourmaline from the Au mineralization and from the Petäjäskoski Formation has similar compositional trends. Mg is the major substituent for Al; inferred low Fe3+/Fe2+ ratios and Na values (<0.8 atoms per formula unit (apfu)) of all tourmaline samples suggest that they precipitated from reduced, low-salinity fluids. Based on the similar chemical and boron isotope composition and the Re-Os age of molybdenite related to the tourmaline-sulfide-quartz veins, we propose that the tourmaline-forming process is a result of a single magmatic-hydrothermal event related to the extensive granite magmatism at around 1.79-1.77 Ga. Tourmaline was crystallized throughout the hydrothermal process, which resulted in the paragenetic variation between type 1 and type 2. The close association of

  18. Foraminifera in elevated Bermudian caves provide further evidence for +21 m eustatic sea level during Marine Isotope Stage 11

    Science.gov (United States)

    van Hengstum, Peter J.; Scott, David B.; Javaux, Emmanuelle J.

    2009-09-01

    conclusion, we reject the mega-tsunami hypothesis, concur with the +21 m MIS 11 eustatic sea-level hypothesis, and reiterate the need to resolve the disparity between global marine isotopic records and the physical geologic evidence for sea level during MIS 11.

  19. 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

    2017-02-22

    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.

  20. Improved energy confinement with nonlinear isotope effects in magnetically confined plasmas

    CERN Document Server

    Garcia, J; Jenko, F

    2016-01-01

    The efficient production of electricity from nuclear fusion in magnetically confined plasmas relies on a good confinement of the thermal energy. For more than thirty years, the observation that such confinement depends on the mass of the plasma isotope and its interaction with apparently unrelated plasma conditions has remained largely unexplained and it has become one of the main unsolved issues. By means of numerical studies based on the gyrokinetic theory, we quantitatively show how the plasma microturbulence depends on the isotope mass through nonlinear multiscale microturbulence effects involving the interplay between zonal flows, electromagnetic effects and the torque applied. This finding has crucial consequences for the design of future reactors since, in spite of the fact that they will be composed by multiple ion species, their extrapolation from present day experiments heavily relies on the knowledge obtained from a long experimental tradition based in single isotope plasmas.

  1. 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.

  2. 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.

  3. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    a heavy atom vibrates slower than a light atom, the substitution to heavier isotopes in a molecular bond leads to lower Zero-Point Energy (ZPE) and thus amore stable bond. Fromstatistical thermodynamics we know that the influence of ZPE is largest at low temperatures, therefore the clumping of isotopes....... In Papers I and II, isotopically-labeled methane was used and the reactions were studied using Fourier Transform Infrared spectroscopy (FTIR). In Paper III; natural abundance methane was used and only the reaction yield was measured with FTIR spectroscopy. Meanwhile, the isotopic compositions were measured...... the clumping effect by a reaction, the apparent clumpiness is defined as the deviation of the Kinetic Isotope Effect (KIE) of the reaction with the clumped isotope (13CH3D) from the combination of KIEs of reactions with the single substituted isotopologues (13CH4 and 12CH3D). If the KIE of the reaction with 13...

  4. Search for a meteoritic component in impact-melt rocks from the Lonar crater, India - Evidence from osmium isotope systematics

    Science.gov (United States)

    Schulz, T.; Luguet, A.; Koeberl, C.

    2013-12-01

    Introduction: The Lonar crater in western India (Maharashtra) is a bowl-shaped simple impact structure of 1830 m diameter and a depth of 120 m below the rim crest. The crater formed 0.656 × 0.081 Ma ago on the 65 Ma old basaltic lava flows of the Deccan Traps (Jourdan et al. 2010) and is one of the few terrestrial impact structures to have formed in basaltic host-rocks. In the absence of actual meteorite fragments, the impact origin of this structure was supported by the identification of a variety of shock metamorphic features (e.g. Fredriksson et al. 1973). However, clear indications of an extraterrestrial component in impactites based on geochemical studies are absent or remained ambiguous so far (e.g. Osae et al. 2005). As the Os isotope tool has the potential to provide firm constraints on the presence or absence of even very small (meteoritic matter to impactite lithologies (e.g. Koeberl et al. 2002), we conduct a detailed Os isotope study of a variety of unshocked host-basalts (target rocks) and impactites (impact-melt rocks) from the Lonar crater. Samples and Method: All samples analyzed in this study were collected in 2000 and 2001 and were geochemically characterized by Osae et al. (2005). Osmium (and additional PGE) analyses were performed on about 2 g whole rock powders, which were spiked with a mixed 190Os,185Re,191Ir,194Pt tracer, and digested via high pressure Asher using inverse aqua regia. Osmium solvent extraction and microdistillation were performed as described by Cohen and Waters (1996). Osmium isotopic compositions were measured using a TRITON N-TIMS at the Department of Lithospheric Research in Vienna. Results and Discussion: Osmium data on seven target and nine impact melt rocks reveal 187Os/188Os ratios ranging from ~0.38 to ~2.23 for the target rocks and from ~0.22 to ~0.59 for the nine analyzed impact melt rocks, whereas Os concentrations range from ~7.1 to ~31.6 ppt and ~7.2 to ~134 ppt, respectively. Although in the typical range for

  5. A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

    Science.gov (United States)

    Ghosh, S.; Odom, A. L.

    2007-12-01

    Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg

  6. The Effect of Aerosol Formation on Stable Isotopes Ratio in Titan's Atmosphere

    Science.gov (United States)

    Gautier, Thomas; Trainer, Melissa G.; Sebree, Joshua; Wold, Allison; Stern, Jennifer

    2016-10-01

    The formation of large amounts of aerosol in Titan atmosphere induces a significant sink for carbon and nitrogen in the atmosphere. Due to the high complexity of the chemistry leading to aerosol formation, there may be isotopic fractionation along the formation pathways of the aerosol. So far several stable isotopes have been measured in Titan atmosphere including the 13C/12C, 15N/14N and D/H ratios for different gaseous species. However, the fractionation effect of the aerosol formation and its impact on atmospheric stable isotope ratios has yet to be fully understood. Two experimental studies were recently published on the stable carbon [1] and nitrogen [1,2] isotope fractionation during aerosol formation in N2-CH4 reactant mixture. To better constrain the fractionation effect of aerosol formation on the Titan atmosphere we have measured the isotopic fractionation induced in laboratory aerosol analogues produced exploring the space of parameters that are expected to have an effect on fractionation processes. Parameters studied include pressure and temperature of aerosol formation and the reactant gas phase composition, including the standard "Titan" mixture of CH4/N2 as well as other trace species such as benzene (C6H6).[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: C and N Fractionation of CH /N Mixtures during Photochemical Aerosol Formation: Relevance to Titan, (2016) Icarus 270:421-428[2] Kuga, M., Carrasco, N., Marty, B., Marrochi, Y., Bernard, S., Rigaudier, T., Fleury, B., Tissandier, L.: Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles, (2014) EPSL 393:2-13

  7. Determination of Kinetic Isotope Effects in Yeast Alcohol Dehydrogenase Using Transition Path Sampling

    Science.gov (United States)

    Varga, Matthew; Schwartz, Steven

    2015-03-01

    The experimental determination of kinetic isotope effects in enzymatic systems can be a difficult, time-consuming, and expensive process. In this study, we use the Chandler-Bolhius method for the determination of reaction rates within transition path sampling (rTPS) to determine the primary kinetic isotope effect in yeast alcohol dehydrogenase (YADH). In this study, normal mode centroid molecular dynamics (CMD) was applied to the transferring hydride/deuteride in order to correctly incorporate quantum effects into the molecular simulations. Though previous studies have used rTPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. Due to the fact that particle transfer is not wholly indicative of the chemical step, this method cannot be used to determine reaction rate constants in YADH. However, it is possible to determine the transition rate constant of the particle transfer, and the kinetic isotope effect of that step. This method provides a set of tools to determine kinetic isotope effects with the atomistic detail of molecular simulations.

  8. Common pitfalls in statistical analysis: "No evidence of effect" versus "evidence of no effect"

    Directory of Open Access Journals (Sweden)

    Priya Ranganathan

    2015-01-01

    Full Text Available This article is the first in a series exploring common pitfalls in statistical analysis in biomedical research. The power of a clinical trial is the ability to find a difference between treatments, where such a difference exists. At the end of the study, the lack of difference between treatments does not mean that the treatments can be considered equivalent. The distinction between "no evidence of effect" and "evidence of no effect" needs to be understood.

  9. 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

    .1 ± 0.8‰; ε18O, −23.7 ± 1.8‰ to −19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  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. Rubidium isotope effect in superconducting Rb[sub 3]C[sub 60

    Energy Technology Data Exchange (ETDEWEB)

    Burk, B.; Crespi, V.H.; Zettl, A.; Cohen, M.L. (Department of Physics, University of California at Berkeley, Berkeley, California 94720 (United States) Materials Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States))

    1994-06-06

    We have measured the resistive supercondeucting transition temperature in C[sub 60] single crystals intercalated with isotopically pure [sup 87]Rb and [sup 85]Rb and with natural abundance rubidium. We obtain a rubidium isotope effect exponent of [alpha][sub Rb]=[minus]0.028[plus minus]0.036, a result which implies that the Rb-C[sub 60] optic phonons play at most a minor role in the pairing mechanism of Rb[sub 3]C[sub 60].

  12. Comparative isotope ecology of African great apes.

    Science.gov (United States)

    Oelze, Vicky M; Fahy, Geraldine; Hohmann, Gottfried; Robbins, Martha M; Leinert, Vera; Lee, Kevin; Eshuis, Henk; Seiler, Nicole; Wessling, Erin G; Head, Josephine; Boesch, Christophe; Kühl, Hjalmar S

    2016-12-01

    The isotope ecology of great apes is a useful reference for palaeodietary reconstructions in fossil hominins. As extant apes live in C3-dominated habitats, variation in isotope signatures is assumed to be low compared to hominoids exploiting C4-plant resources. However, isotopic differences between sites and between and within individuals are poorly understood due to the lack of vegetation baseline data. In this comparative study, we included all species of free-ranging African great apes (Pan troglodytes, Pan paniscus, Gorilla sp.). First, we explore differences in isotope baselines across different habitats and whether isotopic signatures in apes can be related to feeding niches (faunivory and folivory). Secondly, we illustrate how stable isotopic variations within African ape populations compare to other extant and extinct primates and discuss possible implications for dietary flexibility. Using 701 carbon and nitrogen isotope data points resulting from 148 sectioned hair samples and an additional collection of 189 fruit samples, we compare six different great ape sites. We investigate the relationship between vegetation baselines and climatic variables, and subsequently correct great ape isotope data to a standardized plant baseline from the respective sites. We obtained temporal isotopic profiles of individual animals by sectioning hair along its growth trajectory. Isotopic signatures of great apes differed between sites, mainly as vegetation isotope baselines were correlated with site-specific climatic conditions. We show that controlling for plant isotopic characteristics at a given site is essential for faunal data interpretation. While accounting for plant baseline effects, we found distinct isotopic profiles for each great ape population. Based on evidence from habituated groups and sympatric great ape species, these differences could possibly be related to faunivory and folivory. Dietary flexibility in apes varied, but temporal variation was overall

  13. Isotope effect in the formation of H2 from H2CO studied at the atmospheric simulation chamber SAPHIR

    Directory of Open Access Journals (Sweden)

    R. Koppmann

    2010-06-01

    Full Text Available Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H2 was used to determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecular photolysis channel, and the radical channel has only an indirect effect and cannot be effectively constrained. The molecular channel kinetic isotope effect KIEmol, the ratio of photolysis frequencies j(HCHO→CO+H2/j(HCDO→CO+HD at surface pressure, is determined to be KIEmol=1.63−0.046+0.038. This is similar to the kinetic isotope effect for the total removal of HCHO from a recent relative rate experiment (KIEtot=1.58±0.03, which indicates that the KIEs in the molecular and radical photolysis channels at surface pressure (≈100 kPa may not be as different as described previously in the literature.

  14. Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction

    Directory of Open Access Journals (Sweden)

    Enzo Tiezzi

    2007-09-01

    Full Text Available In this work we present results about the deuterium isotope effect on the globalkinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependenceof the Induction Period upon the percentage of deuterated reactants was found. The isotopiceffect on the bromination reaction of malonic acid was evaluated.

  15. 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

    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...

  16. Isotopic evidence of Middle Proterozoic magmatism from Bombay High Field: Implications to crustal evolution of western offshore of India

    Indian Academy of Sciences (India)

    S S Rathore; A R Vijan; M P Singh; B N Prabhu; Anand Sahu

    2004-03-01

    Precambrian granitic basement rocks obtained from well BH-36 of Bombay High Field, western offshore of India has been studied both by Rb-Sr and K-Ar dating methods. Seven basement samples chosen from two cores have yielded whole rock Rb-Sr isochron age of 1446 ± 67Ma with an initial 87Sr/86Sr ratio of 0.7062 ± 0.0012. This age has been interpreted as the formation/emplacement time of the granite. Two biotite fractions of different grain size separated from a sample CC6B2T have yielded Rb-Sr mineral isochron age of 1385 ± 21 Ma. However, these fractions when studied by K-Ar dating method have yielded slightly higher but mutually consistent ages of 1458 ± 43Ma and 1465 ± 43Ma, respectively. Further, two biotites separated from additional samples CC5B9T and CC6B3B have yielded K-Ar ages of 1452 ± 42Ma and 1425 ± 40Ma with an overall mean age of 1438 ± 19Ma. This mean K-Ar age is indistinguishable from whole rock Rb-Sr isochron as well as mineral isochron age within experimental error. The similarity in the whole rock and biotite ages obtained by different isotopic methods suggests that no thermal disturbance has occurred in these rocks after their emplacement/formation around 1450Ma ago. The present study provides the evidence for the existence of an important Middle Proterozoic magmatic event around 1400-1450Ma on the western offshore of India which, hitherto, was thought to be mainly confined to the eastern Ghats, Satpura and Delhi fold belt of India. This finding may have an important bearing on the reconstruction of Proterozoic crustal evolution of western Indian shield.

  17. 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....

  18. Long-range transport of continentally-derived particulate carbon in the marine atmosphere: evidence from stable carbon isotope studies

    OpenAIRE

    Cachier, Héléne; BUAT-MÉNARD, PATRICK; Fontugne, Michel; Chesselet, Roger

    2011-01-01

    Since 1979, we have investigated marine and non-marine sources of particulate carbon in the marine atmosphere from measurements of carbon concentration and isotopic composition 13C/12C). Aerosol samples were collected, mostly during the Sea/Air Exchange (SEAREX) Program experiments, in the northern and southern hemispheres (Sargasso Sea, Enewetak Atoll, Peru upwelling, American Samoa, New Zealand, Amsterdam Island). The concentration and the isotopic composition of particulate carbon of marin...

  19. 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

  20. Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

    Science.gov (United States)

    Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

  1. Rubidium isotopic composition of the Earth, meteorites, and the Moon: Evidence for the origin of volatile loss during planetary accretion

    Science.gov (United States)

    Pringle, Emily A.; Moynier, Frédéric

    2017-09-01

    Understanding the origin of volatile element variations in the inner Solar System has long been a goal of cosmochemistry, but many early studies searching for the fingerprint of volatile loss using stable isotope systems failed to find any resolvable variations. An improved method for the chemical purification of Rb for high-precision isotope ratio measurements by multi-collector inductively-coupled-plasma mass-spectrometry. This method has been used to measure the Rb isotopic composition for a suite of planetary materials, including carbonaceous, ordinary, and enstatite chondrites, as well as achondrites (eucrite, angrite), terrestrial igneous rocks (basalt, andesite, granite), and Apollo lunar samples (mare basalts, alkali suite). Volatile depleted bodies (e.g. HED parent body, thermally metamorphosed meteorites) are enriched in the heavy isotope of Rb by up to several per mil compared to chondrites, suggesting volatile loss by evaporation at the surface of planetesimals. In addition, the Moon is isotopically distinct from the Moon in Rb. The variations in Rb isotope compositions in the volatile-poor samples are attributed to volatile loss from planetesimals during accretion. This suggests that either the Rb (and other volatile elements) were lost during or following the giant impact or by evaporation earlier during the accretion history of Theia.

  2. Isotope effects in the non enzymic glycation of hemoglobin catalyzed by DPG

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Herminia; Uzcategui, Jorge [Universidad de Los Andes, Merida (Venezuela). Dept. de Quimica

    1993-12-31

    The paradigmatic reaction of glucose with hemoglobin (Hb A{sub o}) has been studied and is known to occur most rapidly at the N-terminal valine of the {beta}-subunit. An initial, rapid imine formation is succeeded by slower Amadori rearrangement. Non enzymic glycation of Hb A{sub o} was studied in vitro in buffer Tris 10 mM in H{sub 2} O and D{sub 2} O, pH 7.3, pD 7.8 at 37 deg C at a fixed concentration of 2,3 diphosphoglycerate (DPG). The reaction exhibits identical rates in protium and deuterium oxides. When D-glucose-2-h is compared with D-glucose-2-d, the kinetic isotope effect for the DPG-dependent rate is 2.1 {+-} 0.3, while the DPG-independent rate constant shows no isotope effect (1.1 {+-} 0.1). The absence of a rate in isotopic water solvents shows that proton donation for solvent, lyons or DPG does not limit the rate. The substrate isotope effect of around 2 for the DPG kinetic term indicates that the proton abstraction step of the Amadori rearrangement by DPG is wholly or partially rate-limiting for this reaction. (author) 23 refs., 4 figs.

  3. Oxygen Isotope Effect and Structural Phase Transitions in La2CuO4-Based Superconductors.

    Science.gov (United States)

    Crawford, M K; Farneth, W E; McCarronn, E M; Harlow, R L; Moudden, A H

    1990-12-07

    The oxygen isotope effect on the superconducting transition temperature (alpha(o)) varies as a function of x in La2-xSrxCuO(4) and La2-xBaxCuO(4), with the maximum alpha(o) values (alpha(o) >/= 0.5) found for x near 0.12. This unusual x dependence implies that the isotope effect is influenced by proximity to the Abma --> P4(2)/ncm structural phase transition in these systems. Synchrotron x-ray difaction measurements reveal little change in lattice parameters or orthorhombicity due to isotope exchange in strontium-doped materials where alpha(o) > 0.5, eliminating static structural distortion as a cause of the large isotope effects. The anomalous behavior of alpha(o) in both strontium- and barium-doped materials, in combination with the previously discovered Abma --> P4(2)/ncm structural phase-transition in La(1.88)B(0.12)CuO(4), suggests that an electronic contribution to the lattice instability is present and maximizes at approximately 1/8 hole per copper atom. These observations indicate a dose connection between hole doping of the Cu-O sheets, tilting instabilities of the CuO(6) octahedra, and superconductivity in La(2)CuO(4)-based superconductors.

  4. An unusual isotope effect in a high-transition-temperature superconductor.

    Science.gov (United States)

    Gweon, G-H; Sasagawa, T; Zhou, S Y; Graf, J; Takagi, H; Lee, D-H; Lanzara, A

    2004-07-08

    In conventional superconductors, the electron pairing that allows superconductivity is caused by exchange of virtual phonons, which are quanta of lattice vibration. For high-transition-temperature (high-T(c)) superconductors, it is far from clear that phonons are involved in the pairing at all. For example, the negligible change in T(c) of optimally doped Bi2Sr2CaCu2O8+delta (Bi2212; ref. 1) upon oxygen isotope substitution (16O --> 18O leads to T(c) decreasing from 92 to 91 K) has often been taken to mean that phonons play an insignificant role in this material. Here we provide a detailed comparison of the electron dynamics of Bi2212 samples containing different oxygen isotopes, using angle-resolved photoemission spectroscopy. Our data show definite and strong isotope effects. Surprisingly, the effects mainly appear in broad high-energy humps, commonly referred to as 'incoherent peaks'. As a function of temperature and electron momentum, the magnitude of the isotope effect closely correlates with the superconducting gap--that is, the pair binding energy. We suggest that these results can be explained in a dynamic spin-Peierls picture, where the singlet pairing of electrons and the electron-lattice coupling mutually enhance each other.

  5. 13C/12C and 15N/14N isotope analysis to characterize degradation of atrazine: evidence from parent and daughter compound values.

    Science.gov (United States)

    Meyer, Armin H; Elsner, Martin

    2013-07-02

    Atrazine (Atz) and its metabolite desethylatrazine (DEA) frequently occur in the environment. Conclusive interpretation of their transformation is often difficult. This study explored evidence from (13)C/(12)C and (15)N/(14)N isotope trends in parent and daughter compounds when Atz was dealkylated by (i) permanganate and (ii) the bacterium Rhodococcus sp. NI86/21. In both transformations, (13)C/(12)C ratios of atrazine increased strongly (ε(carbon/permanganate) = -4.6 ± 0.6‰ and ε(carbon/Rhodoccoccus) = -3.8 ± 0.2‰), whereas nitrogen isotope fractionation was small. (13)C/(12)C ratios of DEA showed the following trends. (i) When DEA was formed as the only product (Atz + permanganate), (13)C/(12)C remained constant, close to the initial value of Atz, because the carbon atoms involved in the reaction step are not present in DEA. (ii) When DEA was formed together with desisopropylatrazine (biodegradation of Atz), (13)C/(12)C increased but only within 2‰. (iii) When DEA was further biodegraded, (13)C/(12)C increased by up to 9‰ giving strong testimony of the metabolite's breakdown. Two lines of evidence emerge. (a) Enrichment of (13)C/(12)C in DEA, compared to initial Atz, may contain evidence of further DEA degradation. (b) Dual element ((15)N/(14)N versus (13)C/(12)C) isotope plots for dealkylation of atrazine agree with indirect photodegradation but differ from direct photolysis and biotic hydrolysis. Trends in multielement isotope data of atrazine may, therefore, decipher different degradation pathways.

  6. Soil organic carbon dynamics under long-term fertilization in a black soil of China: Evidence from stable C isotopes.

    Science.gov (United States)

    Dou, Xiaolin; He, Ping; Zhu, Ping; Zhou, Wei

    2016-01-01

    Effects of different fertilizers on organic carbon (C) storage and turnover of soil fractions remains unclear. We combined soil fractionation with isotope analyses to examine soil organic carbon (SOC) dynamics after 25 years of fertilization. Five types of soil samples including the initial level (CK) and four fertilization treatments (inorganic nitrogen fertilizer, N; balanced inorganic fertilizer, NPK; inorganic fertilizer plus farmyard manure, MNPK; inorganic fertilizer plus corn straw residue, SNPK) were separated into four aggregate sizes (>2000 μm, 2000-250 μm, 250-53 μm, and organic matter (iPOM), and mineral-associated organic matter (mSOM). Physical fractionation showed the iPOM fraction of aggregates dominated C storage, averaging 76.87% of SOC storage. Overall, application of N and NPK fertilizers cannot significantly increase the SOC storage but enhanced C in mSOM of aggregates, whereas MNPK fertilizer resulted in the greatest amount of SOC storage (about 5221.5 g C m(2)) because of the enhanced SOC in LF, iPOM and mSOM of each aggregate. The SNPK fertilizer increased SOC storage in >250 μm aggregates but reduced SOC storage in <250 μm aggregates due to SOC changes in LF and iPOM.

  7. Quantum-instanton evaluation of the isotopic effects on the rate constants

    Science.gov (United States)

    Vanicek, Jiri; Miller, William H.

    2004-03-01

    We present a general quantum-mechanical method suitable for numerical evaluation of the isotopic effects on the rate constants of chemical reactions. Our method is based on the quantum instanton approximation [1-3] and on the path-integral Metropolis Monte-Carlo evaluation of the Boltzmann operator matrix elements. The method is more accurate than existing transition-state theory or semiclassical instanton method since we do not assume a single reaction path and do not use a semiclassical approximation of the Boltzmann operator. In order to calculate the isotopic effect we use a "charging algoritm," whereby the mass of the isotope is continuously changed from the initial to the final value. Direct calculation of the isotopic ratio turns out to be much more efficient than finding the absolute rate constants first and then calculating their ratio. While the Monte-Carlo implementation should make the method accessible to systems with a larger number of atoms, we present numerical results for the Eckart barrier and for the reactions H + H2 arrow H2 + H and H + DH arrow HD + H. [1] W.H. Miller, Y. Zhao, M. Ceotto, and Sandy Yang, J. Chem. Phys. 119, 1329 (2003). [2] T. Yamamoto and W.H. Miller, J. Chem. Phys. (in press). [3] Y. Zhao, T. Yamamoto, and W.H. Miller, J. Chem. Phys. (in press).

  8. Soil Drying Effects on the Carbon Isotope Composition of Soil Respiration

    Science.gov (United States)

    Phillips, C. L.; Nickerson, N.; Risk, D.; Kayler, Z. E.; Rugh, W.; Mix, A. C.; Bond, B. J.

    2008-12-01

    -steady-state effects are necessary to avoid spurious correlations between measured δ13CO2 and soil moisture. A third experiment, using closed-system soil incubations to avoid non-steady state mixing with atmospheric CO2, indicates that the isotopic composition of microbial soil respiration appears to be unchanging under a large range of soil moisture contents.

  9. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

    Science.gov (United States)

    Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

    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 ((15)N, (17)O, and (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(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-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 (15)ɛ = (-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 (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the

  10. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Science.gov (United States)

    Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

    2014-06-01

    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 (15N, 17O, and 18O) 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 (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-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 15ɛ = (-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 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well

  11. 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

  12. U-Pb isotopic ages and Hf isotope composition of zircons in Variscan gabbros from central Spain: evidence of variable crustal contamination

    Science.gov (United States)

    Villaseca, Carlos; Orejana, David; Belousova, Elena; Armstrong, Richard A.; Pérez-Soba, Cecilia; Jeffries, Teresa E.

    2011-03-01

    Ion microprobe U-Pb analyses of zircons from three gabbroic intrusions from the Spanish Central System (SCS) (Talavera, La Solanilla and Navahermosa) yield Variscan ages (300 to 305 Ma) in agreement with recent studies. Only two zircon crystals from La Solanilla massif gave slightly discordant Paleoproterozoic ages (1,848 and 2,010 Ma). Hf isotope data show a relatively large variation with the juvenile end-members showing ɛHfi values as high as +3.6 to +6.9 and +1.5 to +2.9 in the Navahermosa and Talavera gabbros, respectively. These positive ɛHfi values up to +6.9 might represent the composition of the subcontinental mantle which generates these SCS gabbros. This ɛHfi range is clearly below depleted mantle values suggesting the involvement of enriched mantle components on the origin of these Variscan gabbros, and is consistent with previous whole-rock studies. The presence of zircons with negative ɛHfi values suggest variable, but significant, crustal contamination of the gabbros, mainly by mixing with coeval granite magmas. Inherited Paleoproterozoic zircons of La Solanilla gabbros have similar trace element composition (e.g. Th/U ratios), but more evolved Hf-isotope signatures than associated Variscan zircons. Similar inherited ages have been recorded in zircons from coeval Variscan granitoids from the Central Iberian Zone. Granitic rocks have Nd model ages (TDM) predominantly in the range of 1.4 to 1.6 Ga, suggesting a juvenile addition during the Proterozoic. However, Hf crustal model ages of xenocrystic Proterozoic zircons in La Solanilla gabbro indicate the presence of reworked Archean protoliths (TDM2 model ages of 3.0 to 3.2 Ga) incorporated into the hybridized mafic magma.

  13. Pleistocene paleo-groundwater as a pristine fresh water resource in southern Germany – evidence from stable and radiogenic isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Geldern, Robert van, E-mail: robert.van.geldern@fau.de [Friedrich-Alexander-University Erlangen-Nuremberg (FAU), Department of Geography and Geosciences, GeoZentrum Nordbayern, Schlossgarten 5, 91054 Erlangen (Germany); Baier, Alfons; Subert, Hannah L. [Friedrich-Alexander-University Erlangen-Nuremberg (FAU), Department of Geography and Geosciences, GeoZentrum Nordbayern, Schlossgarten 5, 91054 Erlangen (Germany); Kowol, Sigrid [Erlanger Stadtwerke AG, Äußere Brucker Str. 33, 91052 Erlangen (Germany); Balk, Laura; Barth, Johannes A.C. [Friedrich-Alexander-University Erlangen-Nuremberg (FAU), Department of Geography and Geosciences, GeoZentrum Nordbayern, Schlossgarten 5, 91054 Erlangen (Germany)

    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. - 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.

  14. A Review of the Isotopic and Trace Element Evidence for Mantle and Crustal Processes in the Hadean and Archean: implications for the Onset of Plate Tectonic Subduction

    Science.gov (United States)

    Smart, Katie A.; Tappe, Sebastian; Stern, Richard A.; Webb, Susan J.; Ashwal, Lewis D.

    2016-03-01

    Plate tectonics plays a vital role in the evolution of our planet. Geochemical analysis of Earth’s oldest continental crust suggests that subduction may have begun episodically about 3.8 to 3.2 billion years ago, during the early Archaean or perhaps more than 3.8 billion years ago, during the Hadean. Yet, mantle rocks record evidence for modern-style plate tectonics beginning only in the late Archaean, about 3 billion years ago. Here we analyse the nitrogen abundance, as well as the nitrogen and carbon isotopic signatures of Archaean placer diamonds from the Kaapvaal craton, South Africa, which formed in the upper mantle 3.1 to 3.5 billion years ago. We find that the diamonds have enriched nitrogen contents and isotopic compositions compared with typical mantle values. This nitrogen geochemical fingerprint could have been caused by contamination of the mantle by nitrogen-rich Archaean sediments. Furthermore, the carbon isotopic signature suggests that the diamonds formed by reduction of an oxidized fluid or melt. Assuming that the Archaean mantle was more reduced than the modern mantle, we argue that the oxidized components were introduced to the mantle by crustal recycling at subduction zones. We conclude, on the basis of evidence from mantle-derived diamonds, that modern-style plate tectonics operated as early as 3.5 billion years ago.

  15. Stable Carbon and Nitrogen Isotope Evidence in Human Diets Based on Evidence from the Jiangzhai Site, China%姜寨遗址先民食谱分析

    Institute of Scientific and Technical Information of China (English)

    郭怡; 胡耀武; 高强; 王昌燧; Michael P.Richards

    2011-01-01

    尽管通过C、N稳定同位素分析已对陕西临潼姜寨遗址先民的食物结构和粟作农业进行了初步探索,但研究中的一些重要问题,如不同时期先民食物结构的演变,姜寨与半坡、史家先民食物结构间的差异等,依然未能深入讨论.为此,本文对姜寨遗址出土的不同时期(一期、二期)人骨进行了C、N稳定同位素分析,试图揭示先民食物结构的演变历程,探索姜寨与半坡、史家先民食物结构间的差异,并初步探讨产生这种差异的可能原因.人骨的δ13C平均值(-9.7±1.0‰)和δ15N平均值(8.5±0.5‰),表明粟类食物(包括粟类作物以及依赖于粟类作物的动物等)在姜寨先民食谱中占据主要地位,且动物资源在食物中的比例相对较低.两期先民的δ13C和δ15N值,无显著性差异,表明先民一直从事粟作农业以及家畜的饲养活动.食谱分析并未发现第二期先民食用更多野生动物的证据,这可能与先民样品量相对偏少、二期先民食用的野生动物比例上升较小、动物类食物在先民食谱中所占比例较小等原因有关.对比地理位置毗邻、文化年代相近的姜寨、史家、半坡遗址先民δ13C值,姜寨(-9.7±1.0‰,N=19)与史家(-10.0±0.7‰,N =9)接近,而远高于半坡(-14.8±1.9‰,N=5),表明半坡遗址粟作农业的种植规模要逊于姜寨和史家遗址.我们认为,不同遗址间先民δ13C值的差异,可能受半坡样品量偏少、遗址间小生态环境不同等因素的影响.%Abstract: Although human dietary evidence from the Jiangzhai site has already been investigated, there are some important issues that have not been discussed clearly, such as whether these human diets changed between periods, and whether there were any differences in human diets among the Banpo, Shijia and Jiangzhai sites. Considering these concerns, stable carbon and nitrogen isotopic analysis on ancient human bones from the Jiangzhai site was

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

    Energy Technology Data Exchange (ETDEWEB)

    DePaolo, D.J.; Kyte, F.T.; Marshall, B.D.; O' Neil, J.R.; Smit, J.

    1983-09-01

    Isotopic ratios and trace element abundances were measured on samples of IR-enriched clay at the Cretaceous-Tertiary boundary, and in carbonate and marl from 5 cm below and 3 cm above the boundary. Samples were leached with acetic acid to remove carbonate, and with hydrochloric acid. Leachates and residues were measured. The Sr, Nd, O and H isotopic compositions of the boundary clay residues are distinct from those of the stratigraphically neighboring materials. The data indicate that most of the clay material was derived from a terrestrial source with relatively low /sup 87/Sr//sup 86/Sr and high /sup 143/Nd//sup 144/Nd ratios. The delta/sup 18/O data suggest that the detritus has been modified by submarine weathering. K-Ca and Rb-Sr systematics, as well as O isotope ratios of K-feldspar spherules within the boundary clay, suggest that they are predominantly authigenic and may have formed after the time of deposition. However, Sm-Nd and Rb-Sr isotopic data indicate that the spherules contain relict material that provides information on the nature of the original detritus. The isotopic evidence for foreign terrestrial detritus in the boundary clay, the low rare earth element concentrations and high Ni concentration, support the hypothesis of a terminal Cretaceous asteroidal impact that produced a global layer of fallout. The data are most easily explained if the impact sites was on oceanic crust rather than continental crust, and if a substantial fraction of the fallout was derived from relatively deep within the lithosphere (> 3 km). This would probably require a single large impactor. 60 references.

  17. Molybdenum isotopic evidence for the origin of chondrules and a distinct genetic heritage of carbonaceous and non-carbonaceous meteorites

    Science.gov (United States)

    Budde, Gerrit; Burkhardt, Christoph; Brennecka, Gregory A.; Fischer-Gödde, Mario; Kruijer, Thomas S.; Kleine, Thorsten

    2016-11-01

    Nucleosynthetic isotope anomalies are powerful tracers to determine the provenance of meteorites and their components, and to identify genetic links between these materials. Here we show that chondrules and matrix separated from the Allende CV3 chondrite have complementary nucleosynthetic Mo isotope anomalies. These anomalies result from the enrichment of a presolar carrier enriched in s-process Mo into the matrix, and the corresponding depletion of this carrier in the chondrules. This carrier most likely is a metal and so the uneven distribution of presolar material probably results from metal-silicate fractionation during chondrule formation. The Mo isotope anomalies correlate with those reported for W isotopes on the same samples in an earlier study, suggesting that the isotope variations for both Mo and W are caused by the heterogeneous distribution of the same carrier. The isotopic complementary of chondrules and matrix indicates that both components are genetically linked and formed together from one common reservoir of solar nebula dust. As such, the isotopic data require that most chondrules formed in the solar nebula and are not a product of protoplanetary impacts. Allende chondrules and matrix together with bulk carbonaceous chondrites and some iron meteorites (groups IID, IIIF, and IVB) show uniform excesses in 92Mo, 95Mo, and 97Mo that result from the addition of supernova material to the solar nebula region in which these carbonaceous meteorites formed. Non-carbonaceous meteorites (enstatite and ordinary chondrites as well as most iron meteorites) do not contain this material, demonstrating that two distinct Mo isotope reservoirs co-existed in the early solar nebula that remained spatially separated for several million years. This separation was most likely achieved through the formation of the gas giants, which cleared the disk between the inner and outer solar system regions parental to the non-carbonaceous and carbonaceous meteorites. The Mo isotope

  18. New triple oxygen isotope data of bulk and separated fractions from SNC meteorites: Evidence for mantle homogeneity of Mars

    Science.gov (United States)

    Ali, Arshad; Jabeen, Iffat; Gregory, David; Verish, Robert; Banerjee, Neil R.

    2016-05-01

    We report precise triple oxygen isotope data of bulk materials and separated fractions of several Shergotty-Nakhla-Chassigny (SNC) meteorites using enhanced laser-assisted fluorination technique. This study shows that SNCs have remarkably identical Δ17O and a narrow range in δ18O values suggesting that these meteorites have assimilated negligibly small surface materials (<5%), which is undetectable in the oxygen isotope compositions reported here. Also, fractionation factors in coexisting silicate mineral pairs (px-ol and mask-ol) further demonstrate isotopic equilibrium at magmatic temperatures. We present a mass-dependent fractionation line for bulk materials with a slope of 0.526 ± 0.016 (1SE) comparable to the slope obtained in an earlier study (0.526 ± 0.013; Franchi et al. 1999). We also present a new Martian fractionation line for SNCs constructed from separated fractions (i.e., pyroxene, olivine, and maskelynite) with a slope of 0.532 ± 0.009 (1SE). The identical fractionation lines run above and parallel to our terrestrial fractionation line with Δ17O = 0.318 ± 0.016‰ (SD) for bulk materials and 0.316 ± 0.009‰ (SD) for separated fractions. The conformity in slopes and Δ17O between bulk materials and separated fractions confirm oxygen isotope homogeneity in the Martian mantle though recent studies suggest that the Martian lithosphere may potentially have multiple oxygen isotope reservoirs.

  19. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-15

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

  1. Fluid inclusion and H-O isotope evidence for immiscibility during mineralization of the Yinan Au-Cu-Fe deposit, Shandong, China

    Science.gov (United States)

    Zhang, Y. M.; Gu, X. X.; Liu, L.; Dong, S. Y.; Li, K.; Li, B. H.; Lv, P. R.

    2011-07-01

    The fluid inclusion and H-O isotope studies have provided the evidences for the source of ore-forming fluids, and helped to recognize two types of immiscibility and their relationships with mineralization. Hydrogen and oxygen isotopic geochemistry shows that the earlier ore-forming fluids during the anhydrous skarn stage (I) and the hydrous skarn-magnetite stage (II) were mainly derived from magmatic water, while the later fluids during the quartz-sulfide stage (III) and the carbonate stage (IV) were mainly from magmatic water mixed with small amounts of meteoric water. Various types of fluid inclusions, including abundant vapor- or liquid-rich two-phase aqueous inclusions, daughter minerals-bearing multiphase inclusions, CO 2-H 2O inclusions, and less abundant liquid inclusions, vapor inclusions and melt inclusions, are present in hydrothermal minerals of different stages. The liquid-vapor fluid inclusions are mainly composed of H 2O, with significant amounts of CO 2 and a small amount of CH 4. In the opaque-bearing fluid inclusions, the hematite and fahlore (tetrahedrite) were identified. The homogenization temperature of the aqueous fluid inclusions decreases from Stage I (520-410 °C), through Stage II (430-340 °C) and III (250-190 °C), to Stage IV (190-130 °C). The coexistence of melt inclusions with simultaneously trapped vapor- or liquid-rich two-phase aqueous inclusions and daughter minerals-bearing multiphase inclusions in garnet, diopside and epidote of Stages I and II suggests an immiscibility between silicate melt and hydrothermal fluid. It is an effective mechanism on scavenging and transporting ore-forming components from magmas. The aqueous fluid inclusions with various vapor/liquid ratios (from 65%) commonly coexist with simultaneously trapped liquid inclusions, vapor inclusions, daughter minerals-bearing multiphase inclusions and CO 2-H 2O inclusions in the quartz of Stage III, and the different kinds of the fluid inclusions have similar

  2. 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)

  3. Petrographic, geochemical and isotopic evidence of crustal assimilation processes in the Ponte Nova alkaline mafic-ultramafic massif, SE Brazil

    Science.gov (United States)

    Azzone, Rogério Guitarrari; Montecinos Munoz, Patricio; Enrich, Gaston Eduardo Rojas; Alves, Adriana; Ruberti, Excelso; Gomes, Celsode Barros

    2016-09-01

    Crustal assimilation plus crystal fractionation processes of different basanite magma batches control the evolution of the Ponte Nova cretaceous alkaline mafic-ultramafic massif in SE Brazil. This massif is composed of several intrusions, the main ones with a cumulate character. Disequilibrium features in the early-crystallized phases (e.g., corrosion and sieve textures in cores of clinopyroxene crystals, spongy-cellular-textured plagioclase crystals, gulf corrosion texture in olivine crystals) and classical hybridization textures (e.g., blade biotite and acicular apatite crystals) provide strong evidence of open-system behavior. All samples are olivine- and nepheline-normative rocks with basic-ultrabasic and potassic characters and variable incompatible element enrichments. The wide ranges of whole-rock 87Sr/86Sri and 143Nd/144Ndi ratios (0.70432-0.70641 and 0.512216-0.512555, respectively) are indicative of crustal contribution from the Precambrian basement host rocks. Plagioclase and apatite 87Sr/86Sr ratios (0.70422-0.70927) obtained for the most primitive samples of each intrusion indicate disequilibrium conditions from early- to principal-crystallization stages. Isotope mixing-model curves between the least contaminated alkaline basic magma and heterogeneous local crustal components indicate that each intrusion of the massif is differentiated from the others by varied degrees of crustal contribution. The primary mechanisms of crustal contribution to the Ponte Nova massif involve the assimilation of host rock xenoliths during the development of the chamber environment and the assimilation of partial melts from the surrounding host rocks. Thermodynamic models using the melts algorithm indicate that parental alkaline basic magmas can be strongly affected by contamination processes subsequently to their initial stages of crystallization when there is sufficient energy to assimilate partial melts of crustal host rocks. The assimilation processes are considered to

  4. Nitrogen isotopic evidence for a shift from nitrate- to diazotroph-fueled export production in VAHINE mesocosm experiments

    Directory of Open Access Journals (Sweden)

    A. N. Knapp

    2015-12-01

    Full Text Available In a shallow, coastal lagoon off the southwest coast of New Caledonia, large-volume (~ 50 m3 mesocosm experiments were undertaken to track the fate of newly fixed nitrogen (N. The mesocosms were intentionally fertilized with 0.8 μM dissolved inorganic phosphorus (DIP to stimulate diazotrophy. N isotopic evidence indicates that the dominant source of N fueling export production shifted from subsurface nitrate (NO3− assimilated prior to the start of the 23 day experiments to N2 fixation by the end of the experiments. While the δ15N of the sinking particulate N (PNsink flux changed during the experiments, the δ15N of the suspended PN (PNsusp and dissolved organic N (DON pools did not. This is consistent with previous observations that the δ15N of surface ocean N pools is less responsive than that of PNsink to changes in the dominant source of new N to surface waters. In spite of the absence of detectable NO3− in the mesocosms, the δ15N of PNsink indicated that NO3− continued to fuel a significant fraction of export production (20 to 60 % throughout the 23 day experiments, with N2 fixation dominating export after about two weeks. The low rates of primary productivity and export production during the first 14 days were primarily supported by NO3−, and phytoplankton abundance data suggest that export was driven by large diatoms sinking out of surface waters. Concurrent molecular and taxonomic studies indicate that the diazotroph community was dominated by diatom-diazotroph assemblages (DDAs at this time. However, these DDAs represented a minor fraction (2 fixation; they were thus not important for driving export production, either directly or indirectly. The unicellular cyanobacterial diazotroph, a Cyanothece-like UCYN-C, proliferated during the last phase of the experiments when N2 fixation, primary production, and the flux of PNsink increased significantly, and δ15N budgets reflected a predominantly diazotrophic source of N fueling

  5. Cooper pair breaking and isotope effect coefficient variation in high-T{sub c} superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S.P.; Pandey, R.K.; Singh, P. [G.B. Pant Univ. Pantanagar, Nainital (India)

    1996-06-01

    The effect of pair breaking on the isotope effect coefficient a = {minus}d ln T{sub c}/d ln M in La{sub 2{minus}x}Sr{sub x}CuO{sub 4} and Pr-, Ca-, and Zn-doped YBa{sub 2}Cu{sub 3}O{sub 7{minus}x} and EuBa{sub 2}Cu{sub 3}O{sub 7{minus}x} is studied using the generalized Abrikosov-Gorkov theory recently employed by Singh and Kishore for superconductivity. It is argued that the isotope effect coefficient a can be further enhanced, in agreement with experimental observation, by considering the dependence of the characteristic scattering time {tau}{sub s} for Cooper pairs on the concentration n of impurities (both magnetic and nonmagnetic) and the disorder ignored by them.

  6. Astronomical Oxygen Isotopic Evidence for Supernova Enrichment of the Solar System Birth Environment by Propagating Star Formation

    CERN Document Server

    Young, Edward D; Smith, Rachel L; Morris, Mark R; Pontoppidan, Klaus M

    2010-01-01

    New infrared absorption measurements of oxygen isotope ratios in CO gas from individual young stellar objects confirm that the solar system is anomalously high in its 18O/17O ratio compared with extra-solar oxygen in the Galaxy. We show that this difference in oxygen isotope ratios is best explained by 1 per cent enrichment of the proto-solar molecular cloud by ejecta from type II supernovae from a cluster having of order a few hundred stars that predated the Sun by at least 10 to 20 Myr. The likely source of exogenous oxygen was the explosion of one or more B stars during a process of propagating star formation.

  7. 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

  8. 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.

  9. The effect of bonding environment on iron isotope fractionation between minerals at high temperature

    Science.gov (United States)

    Sossi, Paolo A.; O'Neill, Hugh St. C.

    2017-01-01

    Central to understanding the processes that drive stable isotope fractionation in nature is their quantification under controlled experimental conditions. The polyvalent element iron, given its abundance in terrestrial rocks, exerts controls on the structural and chemical properties of minerals and melts. The iron isotope compositions of typical high temperature minerals are, however, poorly constrained and their dependence on intensive (e.g. fO2) and extensive (e.g. compositional) variables is unknown. In this work, experiments involving a reference phase, 2 M FeCl2·4H2O(l), together with an oxide mix corresponding to the bulk composition of the chosen mineral were performed in a piston cylinder in Ag capsules. The oxide mix crystallised in situ at 1073 K and 1 GPa, in equilibrium with the iron chloride, and was held for 72 h. In order to characterise the effect of co-ordination and oxidation state on the isotope composition independently, exclusively Fe2+ minerals were substituted in: VIII-fold almandine, VI-fold ilmenite, fayalite and IV-fold chromite and hercynite. Δ57FeMin-FeCl2 increases in the order VIII ion. The composition of the VIFe2+-bearing minerals is similar to that of the aqueous FeCl2 fluid. To the degree that this represents the speciation of iron in fluids exsolving from magmas, the fractionation between them should be small, unless the iron is hosted in magnetite. By contrast, predominantly Fe2+-bearing mantle garnets should preserve a much lighter δ57Fe than their lower pressure spinel counterparts, a signature that may be reflected in partial melts from these lithologies. As the Fe-O bond lengths in fayalite and ilmenite are comparable, their isotope compositions overlap, suggesting that high Ti mare basalts acquired their heavy isotopic signature from ilmenite that crystallised late during lunar magma ocean solidification.

  10. Temperature dependence of the kinetic isotope effect in β-pinene ozonolysis

    Science.gov (United States)

    Gensch, Iulia; Laumer, Werner; Stein, Olaf; Kammer, Beatrix; Hohaus, Thorsten; Saathoff, Harald; Wegener, Robert; Wahner, Andreas; Kiendler-Scharr, Astrid

    2011-10-01

    The temperature dependence of the kinetic isotope effect (KIE) of β-pinene ozonolysis was investigated experimentally at 258, 273 and 303 K in the AIDA atmospheric simulation chamber. Compound specific carbon isotopic analysis of gas phase samples was performed off-line with a Thermo Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS) system. From the temporal behavior of the δ13C of β-pinene a KIE of 1.00358 ± 0.00013 was derived at 303 K, in agreement with literature data. Furthermore, KIE values of 1.00380 ± 0.00014 at 273 K and 1.00539 ± 0.00012 at 258 K were determined, showing an increasing KIE with decreasing temperature. A parameterization of the observed KIE temperature dependence was deduced and used in a sensitivity study carried out with the global chemistry transport model MOZART-3. Two scenarios were compared, the first neglecting, the second implementing the KIE temperature dependence in the simulations. β-Pinene stable carbon isotope ratio and concentration were computed, with emphasis on boreal zones. For early spring it is shown that when neglecting the temperature dependence of KIE, the calculated average age of β-pinene in the atmosphere can be up to two times over- or underestimated. The evolution of the isotopic composition of the major β-pinene oxidation product, nopinone, was examined using Master Chemical Mechanism (MCM) simulations. The tested hypothesis that formation of nopinone and its associated KIE are the determining factors for the observed δ13C values of nopinone is supported at high β-pinene conversion levels.

  11. The effect of paleoecology and paleobiogeography on stable isotopes of Quaternary mammals from South America

    Science.gov (United States)

    Domingo, Laura; Prado, José Luis; Alberdi, María Teresa

    2012-11-01

    The modern South American mammalian assemblage was determined by the closure of the Panama isthmus (˜2.7-3.1 Ma) and later on, by profound climatic and environmental fluctuations occurred during the Quaternary as well as by the appearance of humans in the continent. In the present study, stable isotope analyses (δ13C, δO and δO) have been carried out on Pleistocene-Holocene northern inmigrant and endemic taxa from a broad latitudinal and altitudinal distribution in South America with the purpose of characterizing their paleoecology and the effects of the paleobiogeographic distribution on stable isotope results. Equids and gomphotheres show a wide range of δ13C values going from woodlands to pure C4 grasslands. In the case of equids, Hippidion shows lower δ13C values than Equus in the Late Pleistocene, whereas, in the case of gomphotheres, Cuvieronius and Stegomastodon differ in their δ18O values on account on differences in their paleobiogeography with the former found in the Andean corridor and the latter dispersing through an eastern route. Isotope data of the rest of taxa (immigrant and endemic) are in general in good agreement with other previous isotopic and non-isotopic studies. The latitude threshold between mixed C3-C4 and pure C3 conditions have been pinpointed at ˜33°S in the Middle and the Late Pleistocene. Mammalian δ18O values are intimately related to latitudinal and altitudinal distribution, with the latter exerting an overriding influence independently of latitude. Calculated altitudinal gradients (between -0.23‰/100 m and -0.40‰/100 m) are within the range of modern gradients.

  12. Silicon isotope fractionation during magmatic differentiation

    Science.gov (United States)

    Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Burton, Kevin W.; Halliday, Alex N.

    2011-10-01

    The Si isotopic composition of Earth's mantle is thought to be homogeneous (δ 30Si = -0.29 ± 0.08‰, 2 s.d.) and not greatly affected by partial melting and recycling. Previous analyses of evolved igneous material indicate that such rocks are isotopically heavy relative to the mantle. To understand this variation, it is necessary to investigate the degree of Si isotopic fractionation that takes place during magmatic differentiation. Here we report Si isotopic compositions of lavas from Hekla volcano, Iceland, which has formed in a region devoid of old, geochemically diverse crust. We show that Si isotopic composition varies linearly as a function of silica content, with more differentiated rocks possessing heavier isotopic compositions. Data for samples from the Afar Rift Zone, as well as various igneous USGS standards are collinear with the Hekla trend, providing evidence of a fundamental relationship between magmatic differentiation and Si isotopes. The effect of fractionation has been tested by studying cumulates from the Skaergaard Complex, which show that olivine and pyroxene are isotopically light, and plagioclase heavy, relative to the Si isotopic composition of the Earth's mantle. Therefore, Si isotopes can be utilised to model the competing effects of mafic and felsic mineral fractionation in evolving silicate liquids and cumulates. At an average SiO 2 content of ˜60 wt.%, the predicted δ 30Si value of the continental crust that should result from magmatic fractionation alone is -0.23 ± 0.05‰ (2 s.e.), barely heavier than the mantle. This is, at most, a maximum estimate, as this does not take into account weathered material whose formation drives the products toward lighter δ 30Si values. Mass balance calculations suggest that removal of continental crust of this composition from the upper mantle will not affect the Si isotopic composition of the mantle.

  13. 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.

  14. Effects of preservatives on stable isotope analyses of four marine species

    Science.gov (United States)

    Carabel, Sirka; Verísimo, Patricia; Freire, Juan

    2009-04-01

    The aim of the present study is to quantify the effect of formalin-ethanol preservation on the carbon and nitrogen stable isotope signatures of four taxonomical groups of marine species ( Himanthalia elongata, Anemonia sulcata, Mytilus galloprovincialis and Patella vulgata). To examine temporal changes in the effects of preservation and to determine if preservation induced predictable shifts in δ13C and δ15N signatures, repeated analyses were carried out after 6, 12 and 24 months of preservation. Data from our study showed highly variable effects of the formalin-ethanol preservation on carbon and nitrogen isotope signatures between species. The use of a general correction factor was not possible, or else it should be species-specific. Differences in nitrogen isotopic values between preserved and unpreserved samples were minor compared to the assumed enrichment between trophic levels. The combined use of data from preserved and unpreserved samples could lead to biases in the estimation of the trophic level of organisms. Changes that preservatives caused in carbon values were variable between species and not always small enough to be ignored. So the use of data from preserved samples could change the interpretation of the mixing models used to determine the importance of multiple sources of carbon. In order to elucidate the effects that preservatives have in other species, further studies will be necessary.

  15. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    Methane is an potent greenhouse gas, second only to carbon dioxide of the anthropogenic greenhouse gases in its influence on Earth’s radiative budget. Although less abundant in the atmosphere, methane’s global warming potential is about twentyeight times that of carbon dioxide. Sources of methane...... at significantly different temperatures, therefore, the clumped isotope signatures of methane can be used to identify the process by which the gas was formed. Clumped isotopes can thus be a helpful tool in refining the budget of atmospheric methane. However, the isotopic composition of the atmospheric methane pool....... As is proven in the current research project, the clumped isotopes are removed by oxidation mechanisms at a slower rate. The residual methane pool is therefore enriched in clumped isotopes compared to the methane from the sources. In order to construct a top-down budget of methane, the clumped kinetic effect...

  16. Isotopic evidence for glacial meltwater recharge to the Cambrian-Ordovician aquifer, north-central United States

    Science.gov (United State