Ultralow-loss polaritons in isotopically pure boron nitride

NASA Astrophysics Data System (ADS)

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor; Hoffman, Timothy; Liu, Song; Lindsay, Lucas; Ellis, Chase T.; Assefa, Nathanael; Chatzakis, Ioannis; Reinecke, Thomas L.; Tischler, Joseph G.; Fogler, Michael M.; Edgar, J. H.; Basov, D. N.; Caldwell, Joshua D.

2018-02-01

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called `flat' optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitride (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice

NASA Technical Reports Server (NTRS)

Notesco, G.; Laufer, D.; Bar-Nun, A.; Owen, T.

1999-01-01

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

Method for production of an isotopically enriched compound

DOEpatents

Watrous, Matthew G.

2012-12-11

A method is presented for producing and isolating an isotopically enriched compound of a desired isotope from a parent radionuclide. The method includes forming, or placing, a precipitate containing a parent radionuclide of the desired daughter isotope in a first reaction zone and allowing sufficient time for the parent to decay into the desired gaseous daughter radioisotope. The method further contemplates collecting the desired daughter isotope as a solid in a second reaction zone through the application of temperatures below the freezing point of the desired isotope to a second reaction zone that is connected to the first reaction zone. Specifically, a method is presented for producing isotopically enriched compounds of xenon, including the radioactive isotope Xe-131m and the stable isotope Xe-131.

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

NASA Technical Reports Server (NTRS)

Becker, H.; Walker, R. J.

2003-01-01

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Method for enriching a gaseous isotopic mixture with at least one isotope

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

de Mevergnies, M.N.; Fettweis, P.

1982-02-02

There is described a method for enriching a gas-like isotopic mixture with at least one isotope, in which a mixture of Cf2Cl2 and O2 is irradiated by means of a pulsed and focalized laser beam having an optical frequency corresponding to a wave number lying in the band from 920 to 945 cm-1 to enrich the residual Cf2Cl2 with 37Cl, in the band from 1050 to 1075 cm-1 to produce CoF2 enriched with 13C and/or in the band from 1080 to 1095 cm-1 to enrich the residual Cf2Cl2 with 35Cl and 13C.

Following isotopes in pulse-chase enriched aspen seedlings

NASA Astrophysics Data System (ADS)

Norris, C. E.; Wasylishen, R. E.; Landhäusser, S.; Quideau, S. A.

2011-12-01

One method to quantitatively trace biogeochemical fluxes through ecosystems, such as organic matter decomposition, is to use plant material enriched with stable isotopes. However, as plant macromolecules are known to vary in their rate of formation and decomposition, both the enrichment levels and the location of enrichment within the plant material should be characterized prior to decomposition and tracing studies. Aspen (Populus tremuloides Michx.) is a common tree species with a diverse organic matter chemical structure found in the western Canadian boreal forest. This study used a multi pulse and multi chase enrichment of stable isotopes (15N and 13C) on aspen seedlings to determine the seedling enrichment, isotope movement among plant tissues and translocation of isotopes within plant macromolecules e.g., carbohydrates and lignin. As expected, all tissues experienced increased enrichment with multiple pulses. An initial enrichment with 13C was observed in the leaves followed by translocation to the stems and roots while the 15N moved upward from the roots to leaves. The macromolecular chemistry of the organic carbon was further characterized using 13C solid state nuclear magnetic resonance spectroscopy. After the initial two hour chase period enrichment of the O-alkyl type (carbohydrate) carbon within the leaves was identified, followed by redistribution to more complex carbon compounds after the one week chase period. Root and stem tissues did not show the same pattern. Rather, changes in 13C enrichment were observed in shifting ethyl and methyl alkyl (lipid) carbon peak intensities for the stem samples while roots did not preferentially allocate 13C to a specific macromolecule. These results confirm that stable isotope enrichment of plants was non-uniform across macromolecules and tissue types. Enrichment of aspen seedlings was therefore dependant on the pulse-chase sequence used.

The plasma separation process as a pre-cursor for large scale radioisotope production

NASA Astrophysics Data System (ADS)

Stevenson, Nigel R.

2001-07-01

Radioisotope production generally employs either accelerators or reactors to convert stable (usually enriched) isotopes into the desired product species. Radioisotopes have applications in industry, environmental sciences, and most significantly in medicine. The production of many potentially useful radioisotopes is significantly hindered by the lack of availability or by the high cost of key enriched stable isotopes. To try and meet this demand, certain niche enrichment processes have been developed and commercialized. Calutrons, centrifuges, and laser separation processes are some of the devices and techniques being employed to produce large quantities of selective enriched stable isotopes. Nevertheless, the list of enriched stable isotopes in sufficient quantities remains rather limited and this continues to restrict the availability of many radioisotopes that otherwise could have a significant impact on society. The Plasma Separation Process is a newly available commercial technique for producing large quantities of a wide range of enriched isotopes and thereby holds promise of being able to open the door to producing new and exciting applications of radioisotopes in the future.

Method for laser induced isotope enrichment

DOEpatents

Pronko, Peter P.; Vanrompay, Paul A.; Zhang, Zhiyu

2004-09-07

Methods for separating isotopes or chemical species of an element and causing enrichment of a desired isotope or chemical species of an element utilizing laser ablation plasmas to modify or fabricate a material containing such isotopes or chemical species are provided. This invention may be used for a wide variety of materials which contain elements having different isotopes or chemical species.

The oxygen isotope enrichment of leaf-exported assimilates--does it always reflect lamina leaf water enrichment?

PubMed

Gessler, Arthur; Brandes, Elke; Keitel, Claudia; Boda, Sonja; Kayler, Zachary E; Granier, André; Barbour, Margaret; Farquhar, Graham D; Treydte, Kerstin

2013-10-01

The oxygen stable isotope composition of plant organic matter (OM) (particularly of wood and cellulose in the tree ring archive) is valuable in studies of plant-climate interaction, but there is a lack of information on the transfer of the isotope signal from the leaf to heterotrophic tissues. We studied the oxygen isotopic composition and its enrichment above source water of leaf water over diel courses in five tree species covering a broad range of life forms. We tracked the transfer of the isotopic signal to leaf water-soluble OM and further to phloem-transported OM. Observed leaf water evaporative enrichment was consistent with values predicted from mechanistic models taking into account nonsteady-state conditions. While leaf water-soluble OM showed the expected (18)O enrichment in all species, phloem sugars were less enriched than expected from leaf water enrichment in Scots pine (Pinus sylvestris), European larch (Larix decidua) and Alpine ash (Eucalyptus delegatensis). Oxygen atom exchange with nonenriched water during phloem loading and transport, as well as a significant contribution of assimilates from bark photosynthesis, can explain these phloem (18)O enrichment patterns. Our results indicate species-specific uncoupling between the leaf water and the OM oxygen isotope signal, which is important for the interpretation of tree ring data. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio.

Ultralow-loss polaritons in isotopically pure boron nitride

DOE PAGES

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor; ...

2017-12-11

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called ‘flat’ optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitridemore » (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Lastly, our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.« less

Ultralow-loss polaritons in isotopically pure boron nitride

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

Giles, Alexander J.; Dai, Siyuan; Vurgaftman, Igor

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called ‘flat’ optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitridemore » (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Lastly, our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.« less

Isotope enrichment by frequency-tripled temperature tuned neodymium laser photolysis of formaldehyde

DOEpatents

Marling, John B.

1977-01-01

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation provided by a frequency-tripled, temperature tuned neodymium laser.

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Ion laser isotope enrichment by photo-predissociation of formaldehyde

DOEpatents

Marling, John B.

1977-06-17

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation with a fixed frequency ion laser, specifically, a neon, cadmium, or xenon ion laser.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

A new approach to aid the characterisation and identification of metabolites of a model drug; partial isotope enrichment combined with novel formula elucidation software.

PubMed

Hobby, Kirsten; Gallagher, Richard T; Caldwell, Patrick; Wilson, Ian D

2009-01-01

This work describes the identification of 'isotopically enriched' metabolites of 4-cyanoaniline using the unique features of the software package 'Spectral Simplicity'. The software is capable of creating the theoretical mass spectra for partially isotope-enriched compounds, and subsequently performing an elemental composition analysis to give the elemental formula for the 'isotopically enriched' metabolite. A novel mass spectral correlation method, called 'FuzzyFit', was employed. 'FuzzyFit' utilises the expected experimental distribution of errors in both mass accuracy and isotope pattern and enables discrimination between statistically probable and improbable candidate formulae. The software correctly determined the molecular formulae of ten previously described metabolites of 4-cyanoaniline confirming the technique of partial isotope enrichment can produce results analogous to standard methodologies. Six previously unknown species were also identified, based on the presence of the unique 'designer' isotope ratio. Three of the unknowns were tentatively identified as N-acetylglutamine, O-methyl-N acetylglucuronide and a putative fatty acid conjugate. The discovery of a significant number of unknown species of a model drug with a comprehensive history of investigation highlights the potential for enhancement to the analytical process by the use of 'designer' isotope ratio compounds. The 'FuzzyFit' methodology significantly aided the elucidation of candidate formulae, by provision of a vastly simplified candidate formula data set. Copyright (c) 2008 John Wiley & Sons, Ltd.

Osmium isotope evidence for uniform distribution of s- and r-process components in the early solar system

NASA Astrophysics Data System (ADS)

Yokoyama, Tetsuya; Rai, Vinai K.; Alexander, Conel M. O'D.; Lewis, Roy S.; Carlson, Richard W.; Shirey, Steven B.; Thiemens, Mark H.; Walker, Richard J.

2007-07-01

We have precisely measured Os isotopic ratios in bulk samples of five carbonaceous, two enstatite and two ordinary chondrites, as well as the acid-resistant residues of three carbonaceous chondrites. All bulk meteorite samples have uniform 186Os/ 188Os, 188Os/ 189Os and 190Os/ 189Os ratios, when decomposed by an alkaline fusion total digestion technique. These ratios are also identical to estimates for Os in the bulk silicate Earth. Despite Os isotopic homogeneity at the bulk meteorite scale, acid insoluble residues of three carbonaceous chondrites are enriched in 186Os, 188Os and 190Os, isotopes with major contributions from stellar s-process nucleosynthesis. Conversely, these isotopes are depleted in acid soluble portions of the same meteorites. The complementary enriched and depleted fractions indicate the presence of at least two types of Os-rich components in these meteorites, one enriched in Os isotopes produced by s-process nucleosynthesis, the other enriched in isotopes produced by the r-process. Presolar silicon carbide is the most probable host for the s-process-enriched Os present in the acid insoluble residues. Because the enriched and depleted components present in these meteorites are combined in proportions resulting in a uniform chondritic/terrestrial composition, it requires that disparate components were thoroughly mixed within the solar nebula at the time of the initiation of planetesimal accretion. This conclusion contrasts with evidence from the isotopic compositions of some other elements (e.g., Sm, Nd, Ru, Mo) that suggests heterogeneous distribution of matter with disparate nucleosynthetic sources within the nebula.

On the progressive enrichment of the oxygen isotopic composition of water along a leaf.

PubMed

Farquhar, G. D.; Gan, K. S.

2003-06-01

A model has been derived for the enrichment of heavy isotopes of water in leaves, including progressive enrichment along the leaf. In the model, lighter water is preferentially transpired leaving heavier water to diffuse back into the xylem and be carried further along the leaf. For this pattern to be pronounced, the ratio of advection to diffusion (Péclet number) has to be large in the longitudinal direction, and small in the radial direction. The progressive enrichment along the xylem is less than that occurring at the sites of evaporation in the mesophyll, depending on the isolation afforded by the radial Péclet number. There is an upper bound on enrichment, and effects of ground tissue associated with major veins are included. When transpiration rate is spatially nonuniform, averaging of enrichment occurs more naturally with transpiration weighting than with area-based weighting. This gives zero average enrichment of transpired water, the modified Craig-Gordon equation for average enrichment at the sites of evaporation and the Farquhar and Lloyd (In Stable Isotopes and Plant Carbon-Water Relations, pp. 47-70. Academic Press, New York, USA, 1993) prediction for mesophyll water. Earlier results on the isotopic composition of evolved oxygen and of retro-diffused carbon dioxide are preserved if these processes vary in parallel with transpiration rate. Parallel variation should be indicated approximately by uniform carbon isotope discrimination across the leaf.

Effect of 13C enrichment and sugar type on analysis of sugars by gas chromatography/combustion/isotope ratio mass spectrometry.

PubMed

Baumann, Karen; Dignac, Marie-France; Bardoux, Gérard; Rumpel, Cornelia

2012-09-15

The objective of this investigation was to test gas-chromatographic compound-specific analysis for studies on the isotopic composition of (13)C-enriched sugar molecules. The effects of (13)C enrichment and type of sugar (C5, C6) will provide valuable information on isotopic correction for future studies employing (13)C-enriched sugars. Five sugar solutions of xylose, mannose and glucose with (13)C enrichments ranging between 1.1 and 1.5 atom-% were prepared. The (13)C enrichments of the initial sugars were measured by elemental analyser/isotope ratio mass spectrometry (EA/IRMS); (13)C enrichments for derivatised sugars were obtained by gas chromatography/combustion/IRMS (GC/C/IRMS). The linear relationships between the (13)C enrichments of the initial sugars and the values for the derivatised sugars were sugar-type dependent. Corrections for GC/C/IRMS values took into account the kinetic isotope effect (KIE) of the derivatising agent associated with the coefficient (K(d)) and a newly introduced second coefficient (K(c)) associated with the KIE of the sugar. While K(d) was constant, K(c) varied with sugar type. During derivatisation acetate groups with (12)C and sugars with more (13)C reacted faster. Coefficients for the specific ranges of (13)C enrichments under study have to be assessed and the reactions of different sugar types have to be taken into account to avoid underestimation of (13)C enrichment of up to 9% (C5) or overestimation of up to 4% (C6). Copyright © 2012 John Wiley & Sons, Ltd.

Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Seitz, Hans-Michael

2017-10-01

Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary volcanic rocks of southern Ethiopian rift (Dillo and Megado) reveal the influence of late stage melt-peridotite interaction on the early depleted and variably metasomatized lithospheric mantle. Two types of lherzolites are reported (LREE-depleted La/Sm(N) = 0.11-0.37 × Cl and LREE-enriched, La/Sm(N) = 1.88-15.72 × Cl). The depleted lherzolites have variable range in Li concentration (olivine: 2.1-5.4 ppm; opx: 1.1-2.3 ppm; cpx: 1.0-1.8 ppm) and in Li isotopic composition (δ7Li in olivine: -9.4 to 1.5‰; in opx: -4.5 to 3.6‰; in cpx: -17.0 to 4.8‰), indicating strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The enriched lherzolites have limited range in both Li abundances (olivine: 2.7-3.0 ppm; opx: 1.1-3.1 ppm; cpx: 1.1-2.3 ppm) and Li isotopic compositions (δ7Li in olivine: -1.3 to +1.3‰; in opx: -2.0 to +5.0‰; in cpx: -7.5 to +4.8‰), suggest that the earlier metasomatic event which lead to LREE enrichment could also homogenize the Li contents and its isotopes. The enriched harzburgite and clinopyroxenite minerals show limited variation in Li abundances and variable Li isotopic compositions. The Li enrichments of olivine and clinopyroxene correlate neither with the incompatible trace element enrichment nor with the Sr-Nd isotopic compositions of clinopyroxene. These observations indicate that the metasomatic events which are responsible for the LREE enrichment and for the Li addition are distinct, whereby the LREE-enrichment pre-dates the influx of Li. The presence of large Li isotopic disequilibria within and between minerals of depleted and enriched peridotites suggest that the lithospheric mantle beneath the southern Ethiopian rift has experienced recent melt-peridotite interaction. Thus, the Li data set reported in this study offer new additional evidence for the existence of late stage metasomatism, which probably occurred at shallow depth briefly before and/or during entrainment and ascent of mantle xenoliths to the surface.

An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Popp, Brian N.; Takigiku, Ray; Johnson, Marcus W.

1989-01-01

Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

Isotopic constraints on the origin of meteoritic organic matter

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1991-01-01

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1998-01-01

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Stellar Origins of C-13 and N-15-Enriched Presolar SiC Grains

NASA Technical Reports Server (NTRS)

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.; Wang, Jianhua; Pignatari, Marco; Jose, Jordi; Nguyen, Ann

2016-01-01

Extreme excesses of 13 C ( C (12 C/ 13 C<10) and 15 N ( N (14 N/ 15 N< 20) in rare presolar SiC 20) in rare presolar SiClar SiC grains have been considered diagnostic of an origin in classical novae [1], though an origin in core-collapse supernovae (CCSNe) has also been proposed [2]. We report multi-element isotopic data for 19 13 C- and 15 N-enriched presolar SiC grains(12 C/13 C<16 and 14 N/ 15 N<150) from an acid resistant residue of the Murchison meteorite. These grains are enriched in 13 C and15 N, but with quite diverse Si isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures.

Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, James A.; Hayden, Jr., Howard W.

1995-01-01

An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, J.A.; Hayden, H.W. Jr.

1995-05-30

An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

Implications of 187Os isotopic heterogeneities in a mantle plume: evidence from Gorgona Island and Curaçao

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Storey, Michael; Kerr, Andrew C.; Tarney, John; Arndt, Nicholas T.

1999-03-01

Recent work has suggested that the mafic-ultramafic volcanism in evidence throughout portions of the Caribbean, Central America, and northern South America, including the islands of Gorgona and Curaçao, was generated as part of a middle-Cretaceous, large igneous province. New Re-Os isochron results for tholeiitic basalts from Gorgona and Curaçao indicate crystallization ages of 89.2 ± 5.2 and 85.6 ± 8.1 Ma, respectively, consistent with reported Ar ages. The Gorgona ultramafic suite shows a large range in initial Os isotopic composition, with γ Os values ranging from -0.5 to +12.4. This large range reflects isotopic heterogeneities in the mantle source similar to those observed for modern ocean island basalts. In contrast to ocean island basalts, however, Os isotopic compositions do not correlate with variations in Nd, Sr, or Pb isotopic compositions, which are within the range of depleted mid-ocean ridge basalts. The processes that produced these rocks evidently resulted in the decoupling of Os isotopes from the Nd, Sr, and Pb isotopic systems. Picrites from Curaçao have very uniform, chondritic initial Os isotopic compositions, with initial γ Os values ranging only from -0.4 to ±1.4. Basalts from Curaçao, however, define an isochron with a 187Os-enriched initial isotopic composition (γ Os = +9.5). In contrast to the 187Os-enriched ultramafic rocks from Gorgona, the enrichment in these basalts could have resulted from lithospheric contamination. If the Gorgona and Curaçao rocks were derived from the same plume, Os results, combined with Sr, Nd, and Pb data indicate a heterogeneous plume, with multiple compositionally and isotopically distinct domains. The Os isotopic results require derivation of Os from a minimum of two distinct reservoirs, one with a composition very similar to the chondritic average and one with long-term enriched Re/Os. Oceanic crustal recycling has been invoked to explain most of the 187Os enrichments that have been observed in ocean island basalt sources and could potentially apply to the Gorgona suite. Crustal recycling, however, requires large proportions of very ancient recycled basaltic crust in the sources of the 187Os-enriched ultramafic rocks to explain the magnitude of 187Os enrichments observed. For example, addition of 20% oceanic crust to fertile mantle, and nearly 3 billion years are necessary to generate a reservoir with the Os isotopic composition of the most radiogenic komatiites. If the recycled oceanic crust was added to basalt-depleted mantle, as may be indicated by ɛ Nd values for the komatiites averaging about +10, even larger proportions of older crust are required. Large proportions of oceanic mafic crust in the sources of the 187Os-enriched komatiites, although petrologically conceivable under certain melting conditions, is unlikely here given the limited trace element and lithophile isotope system variations. These results raise questions about the efficacy of using Os isotopes to constrain the proportion of recycled oceanic crust in other plumes. Other possible mechanisms for generating 187Os-enriched mantle include invoking the existence of a 187Os-enriched lower mantle, and minor outer core-lower mantle interactions.

Highly enriched multiply-labeled stable isotopic compounds as atmospheric tracers

DOEpatents

Goldblatt, M.; McInteer, B.B.

1974-01-29

Compounds multiply-labeled with stable isotopes and highly enriched in these isotopes are readily capable of detection in tracer experiments involving high dilutions. Thus, for example, /sup 13/C/sup 18/O/sub 2/ provides a useful tracer for following atmospheric pol lution produced as a result of fossil fuel burning. (Official Gazette)

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

PubMed

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 composition hardly changes even at high temperatures while at drier and warm conditions the enrichment of (18)Ο reaches up to 20‰, depending on the raindrop size and the initial meteorological conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

A new method to track seed dispersal and recruitment using 15N isotope enrichment.

PubMed

Carlo, Tomás A; Tewksbury, Joshua J; Martínez Del Río, Carlos

2009-12-01

Seed dispersal has a powerful influence on population dynamics, genetic structuring, evolutionary rates, and community ecology. Yet, patterns of seed dispersal are difficult to measure due to methodological shortcomings in tracking dispersed seeds from sources of interest. Here we introduce a new method to track seed dispersal: stable isotope enrichment. It consists of leaf-feeding plants with sprays of 15N-urea during the flowering stage such that seeds developed after applications are isotopically enriched. We conducted a greenhouse experiment with Solanum americanum and two field experiments with wild Capsicum annuum in southern Arizona, USA, to field-validate the method. First, we show that plants sprayed with 15N-urea reliably produce isotopically enriched progeny, and that delta 15N (i.e., the isotopic ratio) of seeds and seedlings is a linear function of the 15N-urea concentration sprayed on mothers. We demonstrate that three urea dosages can be used to distinctly enrich plants and unambiguously differentiate their offspring after seeds are dispersed by birds. We found that, with high urea dosages, the resulting delta 15N values in seedlings are 10(3) - 10(4) times higher than the delta 15N values of normal plants. This feature allows tracking not only where seeds arrive, but in locations where seeds germinate and recruit, because delta 15N enrichment is detectable in seedlings that have increased in mass by at least two orders of magnitude before fading to normal delta 15N values. Last, we tested a mixing model to analyze seed samples in bulk. We used the delta 15N values of batches (i.e., combined seedlings or seeds captured in seed traps) to estimate the number of enriched seeds coming from isotopically enriched plants in the field. We confirm that isotope enrichment, combined with batch-sampling, is a cheap, reliable, and user-friendly method for bulk-processing seeds and is thus excellent for the detection of rare dispersal events. This method could further the study of dispersal biology, including the elusive, but critically important, estimation of long-distance seed dispersal.

The Great White Guppy: Top Predator

NASA Astrophysics Data System (ADS)

Michalski, G. M.

2011-12-01

Nitrogen isotopes are often used to trace the trophic level of members of an ecosystem. As part of a stable isotope biogeochemistry and forensics course at Purdue University, students are introduced to this concept by analyzing nitrogen isotopes in sea food purchased from local grocery stores. There is a systematic increase in 15N/14N ratios going from kelp to clams/shrimp, to sardines, to tuna and finally to shark. These enrichments demonstrate how nitrogen is enriched in biomass as predators consume prey. Some of the highest nitrogen isotope enrichments observed, however, are in the common guppy. We investigated a number of aquarium fish foods and find they typically have high nitrogen isotope ratios because they are made form fish meal that is produced primarily from the remains of predator fish such as tuna. From, a isotope perspective, the guppy is the top of the food chain, more ferocious than even the Great White shark.

Separation of sulfur isotopes

DOEpatents

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

1976-06-22

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

A cost-effective approach to produce 15N-labelled amino acids employing Chlamydomonas reinhardtii CC503.

PubMed

Nicolás Carcelén, Jesús; Marchante-Gayón, Juan Manuel; González, Pablo Rodríguez; Valledor, Luis; Cañal, María Jesús; Alonso, José Ignacio García

2017-08-18

The use of enriched stable isotopes is of outstanding importance in chemical metrology as it allows the application of isotope dilution mass spectrometry (IDMS). Primary methods based on IDMS ensure the quality of the analytical measurements and traceability of the results to the international system of units. However, the synthesis of isotopically labelled molecules from enriched stable isotopes is an expensive and a difficult task. Either chemical and biochemical methods to produce labelled molecules have been proposed, but so far, few cost-effective methods have been described. The aim of this study was to use the microalgae Chlamydomonas reinhardtii to produce, at laboratory scale, 15 N-labelled amino acids with a high isotopic enrichment. To do that, a culture media containing 15 NH 4 Cl was used. No kinetic isotope effect (KIE) was observed. The labelled proteins biosynthesized by the microorganism were extracted from the biomass and the 15 N-labelled amino acids were obtained after a protein hydrolysis with HCl. The use of the wall deficient strain CC503 cw92 mt+ is fit for purpose, as it only assimilates ammonia as nitrogen source, avoiding isotope contamination with nitrogen from the atmosphere or the reagents used in the culture medium, and enhancing the protein extraction efficiency compared to cell-walled wild type Chlamydomonas. The isotopic enrichment of the labelled amino acids was calculated from their isotopic composition measured by gas chromatography mass spectrometry (GC-MS). The average isotopic enrichment for the 16 amino acids characterized was 99.56 ± 0.05% and the concentration of the amino acids in the hydrolysate ranged from 18 to 90 µg/mL. Previously reported biochemical methods to produce isotopically labelled proteins have been applied in the fields of proteomics and fluxomics. For these approaches, low amounts of products are required and the isotopic enrichment of the molecules has never been properly determined. So far, only 13 C-labelled fatty acids have been isolated from labelled microalga biomass as valuable industrial products. In this study, we propose Chlamydomonas reinhardtii CC503 as a feasible microorganism and strain to produce labelled biomass from which a standard containing sixteen 15 N-labelled amino acids could be obtained.

A multi-proxy isotope study (δ41K, δ26Mg, 87Sr/86Sr) of low-temperature oceanic crust alteration: the Troodos Ophiolite and Ocean Drilling Program Hole 801C

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

Low-temperature alteration of oceanic crust plays an important role in a number of geochemical cycles, thus modulating the chemical composition of the oceans. In particular, it has been established that low-temperature (<150oC) alteration of basalt is a major sink of seawater potassium. However, little is known about the effects of this process on the potassium isotope composition of seawater, which is 0.5‰ enriched relative to bulk silicate Earth (δ41KBSE=-0.54‰). Here we measure a number of isotope systems (δ41K, δ26Mg, 87Sr/86Sr) in both host rock and vein material from the upper volcanic section of Cretaceous (Troodos Ophiolite) and Jurassic (ODP 801C) oceanic crust using a MC-ICP-MS. The goal is to estimate the K isotopic fractionation associated with basalt alteration in low-temperature conditions, and how it might affect the K isotope enrichment of seawater relative to BSE. We find that marine hydrothermal samples from Troodos and ODP site 801C are enriched in potassium relative to the unaltered glass compositions and have δ41K values both higher and lower than BSE, ranging from -0.45‰ to -0.69‰ (n = 9) and -0.32‰ to -0.71‰ (n = 5), respectively. The low measured δ41K values could represent 1) fractionation (α<1) of K isotopes during uptake from seawater (δ41KSW 0‰), or 2) remobilized mantle-sourced K (δ41KBSE=-0.54‰) from deeper within the ophiolite sequence. Measurements of δ26Mg (n=15) and 87Sr/86Sr (n=12) in these samples yield enriched values relative to bulk silicate Earth, suggesting that alteration of oceanic crust likely happened under high water-to-rock ratios in both Troodos and ODP 801C, and that the added potassium is seawater-sourced. We thus suggest that the isotopically light δ41K values measured in both sites are associated with the formation of secondary clays enriched in the 39K isotope. This light isotope enrichment could be intensified if seawater K sourcing is a diffusion-limited process, as aqueous potassium diffusion has been associated with K isotope fractionations between 0.9967 and 0.9984. Our results indicate that the uptake of potassium in altered oceanic crust could be responsible, in part, for the observed K isotope enrichment of seawater relative to bulk silicate Earth.

Evaluation of sulfur isotopic enrichment of urine metabolites for the differentiation of healthy and prostate cancer mice after the administration of 34S labelled yeast.

PubMed

Galilea San Blas, Oscar; Moreno Sanz, Fernando; Herrero Espílez, Pilar; Sainz Menéndez, Rosa María; Mayo Barallo, Juan Carlos; Marchante-Gayón, Juan Manuel; García Alonso, José Ignacio

2017-01-01

Sulfur isotopic enrichment of urine metabolites in healthy and prostate cancer mice using 34 S enriched yeast and High Performance Liquid Chromatography coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (HPLC-MC-ICP-MS) has been evaluated. A 30 weeks experiment (since the eleventh to the fortieth week of life) was carried out collecting the urine of three healthy mice and three transgenic mice with prostate cancer during 24h after a single oral administration of a 34 S enriched yeast slurry. The isotopic enrichment of different sulphur metabolites was monitored by coupling a C18 reverse phase HPLC column with a multicollector ICP-MS using a membrane desolvating system. Quantification of sulfur in the chromatographic peaks was carried out by post-column isotope dilution using a 33 S enriched spike. Differences between the 34 S enrichment in the urine metabolites of healthy and prostate cancer mice were found from the beginning of the disease. Both populations could be differentiated using a principal component analysis (PCA). Finally, 7 unknown mice were correctly classified in each population using a linear discriminant analysis. Copyright © 2016 Elsevier GmbH. All rights reserved.

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Leaf water 18 O and 2 H enrichment along vertical canopy profiles in a broadleaved and a conifer forest tree.

PubMed

Bögelein, Rebekka; Thomas, Frank M; Kahmen, Ansgar

2017-07-01

Distinguishing meteorological and plant-mediated drivers of leaf water isotopic enrichment is prerequisite for ecological interpretations of stable hydrogen and oxygen isotopes in plant tissue. We measured input and leaf water δ 2 H and δ 18 O as well as micrometeorological and leaf morpho-physiological variables along a vertical gradient in a mature angiosperm (European beech) and gymnosperm (Douglas fir) tree. We used these variables and different enrichment models to quantify the influence of Péclet and non-steady state effects and of the biophysical drivers on leaf water enrichment. The two-pool model accurately described the diurnal variation of leaf water enrichment. The estimated unenriched water fraction was linked to leaf dry matter content across the canopy heights. Non-steady state effects and reduced stomatal conductance caused a higher enrichment of Douglas fir compared to beech leaf water. A dynamic effect analyses revealed that the light-induced vertical gradients of stomatal conductance and leaf temperature outbalanced each other in their effects on evaporative enrichment. We conclude that neither vertical canopy gradients nor the Péclet effect is important for estimates and interpretation of isotopic leaf water enrichment in hypostomatous trees. Contrarily, species-specific non-steady state effects and leaf temperatures as well as the water vapour isotope composition need careful consideration. © 2017 John Wiley & Sons Ltd.

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

PubMed

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.

Pregnancy and Radiation Exposure

MedlinePlus

... pregnant women. Ionizing radiation is the kind of electromagnetic radiation produced by x-ray machines, radioactive isotopes ( ... The reproductive risk of nonionizing radiation, which includes electromagnetic fields emitted from computers, microwave communication systems, microwave ...

Isotopic composition of zinc, copper, and iron in lunar samples

NASA Astrophysics Data System (ADS)

Moynier, F.; Albarède, F.; Herzog, G. F.

2006-12-01

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.

Dual pressure-dual temperature isotope exchange process

DOEpatents

Babcock, D.F.

1974-02-12

A liquid and a gas stream, each containing a desired isotope, flow countercurrently through two liquid-gas contacting towers maintained at different temperatures and pressures. The liquid is enriched in the isotope in one tower while the gas is enriched within the other and a portion of at least one of the enriched streams is withdrawn from the system for use or further enrichment. The tower operated at the lower temperature is also maintained at the lower pressure to prevent formation of solid solvates. Gas flow between the towers passes through an expander-compressor apparatas to recover work from the expansion of gas to the lower pressure and thereby compress the gas returning to the tower of higher pressure. (Official Gazette)

Negative parity states and some electromagnetic transition properties of even-odd erbium isotopes

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

Yazar, Harun Resit; Uluer, Ihsan

2007-03-15

The negative parity states and some electromagnetic transition properties of even-odd erbium isotopes ({sup 159,161,163,165}Er) were studied within the framework of the interacting boson-fermion model. The single fermion is assumed to be in one of the lh{sub 9/2},3p{sub 3/2},2f{sub 5/2}, and 3p{sub 1/2} single-particle orbits. It was found that the calculated negative parity state energy spectra of the even-odd erbium isotopes agree quite well with the experimental data. The B(E2) values were also calculated and compared with the experimental data.

Study of yrast bands and electromagnetic properties in neutron-rich 114-128Cd isotopes

NASA Astrophysics Data System (ADS)

Chaudhary, Ritu; Pandit, Rakesh K.; Devi, Rani; Khosa, S. K.

2018-02-01

The projected shell model framework has been employed to carry out a systematic study on the deformation systematics of E (21+) and E (41+) / E (21+) values, BCS subshell occupation numbers, yrast spectra, backbending phenomena and electromagnetic quantities in 114-128Cd isotopes. Present calculations reproduce the observed systematics of the E (21+), R42 and B (E 2 ;2+ →0+) values for 114-128Cd isotopic mass chain and give the evidence that deformation increases as one moves from 114Cd to 118Cd, thereafter it decreases up to 126Cd. This in turn confirms 118Cd to be the most deformed nucleus in this set of isotopic mass chain. The emergence of backbending, decrease in B (E 2) values and change in g-factors in all these isotopes are intimately related to the crossing of g-band by 2-qp bands.

Correlated Si isotope anomalies and large C-13 enrichments in a family of exotic SiC grains

NASA Technical Reports Server (NTRS)

Stone, J.; Hutcheon, I. D.; Epstein, S.; Wasserburg, G. J.

1991-01-01

A hypothesis is presented to the effect that the distinctive morphological characteristics and comparatively simple Si isotope systematics identify the platy SiC crystals as a genetically related family, formed around a single isotopically heterogeneous presolar star on an association of related stars. The enrichments in C-13 and the Si isotope systematics of the platy SiC are broadly consistent with theoretical models of nucleosynthesis in low-mass, carbon stars on the ASG. The Si isotope array most plausibly reflects mixing between (Si-28)-rich material, inherited from a previous generation of stars, and material enriched in Si-29 and Si-30, produced in intershell regions by neutron capture during He-burning. The absence of a correlation between the Si and C isotopic compositions of the SiC suggests either episodic condensation of SiC, extending over several thermal pulses, in the atmosphere of a single star, or the derivation of the SiC from several stars characterized by different rates of C-13 production.

Formation and Preservation of the Depleted and Enriched Shergottite Isotopic Reservoirs in a Convecting Martian Mantle

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Jones, John H.

2015-01-01

There is compelling isotopic and crater density evidence for geologically recent volcanism on Mars, in the last 100-200 million years and possibly in the last 50 million years. This volcanism is due to adiabatic decompression melting and thus requires some type of present-day convective upwelling in the martian mantle. On the other hand, martian meteorites preserve evidence for at least 3 distinct radiogenic isotopic reservoirs. Anomalies in short-lived isotopic systems (Sm-146, Nd-142, Hf-182, W-182) require that these reservoirs must have developed in the first 50 to 100 million years of Solar System history. The long-term preservation of chemically distinct reservoirs has sometimes been interpreted as evidence for the absence of mantle convection and convective mixing on Mars for most of martian history, a conclusion which is at odds with the evidence for young volcanism. This apparent paradox can be resolved by recognizing that a variety of processes, including both inefficient mantle mixing and geographic separation of isotopic reservoirs, may preserve isotopic heterogeneity on Mars in an actively convecting mantle. Here, we focus on the formation and preservation of the depleted and enriched isotopic and trace element reservoirs in the shergottites. In particular, we explore the possible roles of processes such as chemical diffusion and metasomatism in dikes and magma chambers for creating the isotopically enriched shergottites. We also consider processes that may preserve the enriched reservoir against convective mixing for most of martian history.

Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

PubMed Central

Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

2015-01-01

The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

DOE PAGES

Horkley, J. J.; Carney, K. P.; Gantz, E. M.; ...

2015-03-17

Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore » 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

Kinetic 15N-isotope effects on algal growth

NASA Astrophysics Data System (ADS)

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.

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2015-01-01

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, hypothesized to be the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs, while processes such as fractionating foliar metabolism and preferentially loading into phloem of 13C-enriched sugars may contribute to the overall autotrophic–heterotrophic difference in carbon isotope compositions.« less

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry.

PubMed

Krämer, Lisa; Jäger, Christian; Trezzi, Jean-Pierre; Jacobs, Doris M; Hiller, Karsten

2018-02-14

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13 C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13 C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13 C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13 C-labeled bread and quantified 13 C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated.

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry

PubMed Central

Krämer, Lisa; Jäger, Christian; Jacobs, Doris M.; Hiller, Karsten

2018-01-01

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13C-labeled bread and quantified 13C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated. PMID:29443915

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer.

PubMed

Spence, Michael J; Bottrell, Simon H; Thornton, Steven F; Richnow, Hans H; Spence, Keith H

2005-09-01

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

10 CFR 75.4 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... to IAEA Safeguards) means the collection of environmental samples (e.g., air, water, vegetation, soil... uranium or enriching uranium in the isotope 235, zirconium tubes, heavy water or deuterium, nuclear-grade...); (3) A fuel fabrication plant; (4) An enrichment plant or isotope separation plant for the separation...

Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

DOEpatents

Tanaka, John; Reilly, Jr., James J.

1978-01-01

This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

Accelerator-based method of producing isotopes

DOEpatents

Nolen, Jr., Jerry A.; Gomes, Itacil C.

2015-11-03

The invention provides a method using accelerators to produce radio-isotopes in high quantities. The method comprises: supplying a "core" of low-enrichment fissile material arranged in a spherical array of LEU combined with water moderator. The array is surrounded by substrates which serve as multipliers and moderators as well as neutron shielding substrates. A flux of neutrons enters the low-enrichment fissile material and causes fissions therein for a time sufficient to generate desired quantities of isotopes from the fissile material. The radio-isotopes are extracted from said fissile material by chemical processing or other means.

HIGH ARSENIC CONCENTRATIONS AND ENRICHED SULFUR AND OXYGEN ISOTOPES IN A FRACTURED-BEDROCK GROUND-WATER SYSTEM

EPA Science Inventory

Elevated arsenic concentrations are coincident with enriched sulfur and oxygen isotopes of sulfate in bedrock ground water within Kelly's Cove watershed, Northport, Maine, USA. Interpretation of the data is complicated by the lack of correlations between sulfate concentrations an...

The sources and time-integrated evolution of diamond-forming fluids - Trace elements and isotopic evidence

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Logvinova, Alla; Sobolev, Nikolay V.

2014-01-01

Sub-micrometer inclusions in fibrous diamond growth zones carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The major and trace element patterns of diamond-forming fluids vary widely. Such elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Thus, the combination of elemental and isotope data is a powerful tool in constraining the origin of fluids from which diamonds precipitate. Here we present combined trace element composition (34 diamonds) and Sr isotopic data (23 diamonds) for fluid-rich diamonds from six worldwide locations. The Nd and Pb isotopic composition of two of the diamonds were also obtained. Several of the samples were analyzed in at least 2 locations to investigate variations in the fluid during diamond growth. The data was acquired using an off-line laser sampling technique followed by solution ICPMS and TIMS analysis. The Sr isotopic compositions of diamond fluids from the different suites range between convecting mantle values for Udachnaya (87Sr/86Sr363 = 0.70300 ± 16 to 0.70361 ± 4), to highly enriched values, up to 87Sr/86Sr = 0.72330 ± 3, for a diamond from Congo. No isochronous relationships were observed in any of the suites. The lowest Nd isotopic composition recorded so far in a diamond is from Congo (εNd71 = -40.4), which also contains the most radiogenic Sr isotopic composition. In contrast, a less enriched but still rather unradiogenic Nd isotope composition (εNd540 = -11) was obtained for a diamond from Snap Lake, which has moderately radiogenic Sr isotopic enrichment (87Sr/86Sr540 = 0.70821 ± 1). The Pb isotopic system measured in one diamond indicates a complex evolution for the fluid source, with extreme 207Pb/204Pb ratio (15.810 ± 3) and moderate, kimberlite-like 206Pb/204Pb and 208Pb/204Pb ratios. A multi-stage evolution of the diamond-forming fluids source can be constrained from our new isotopic data, indicating an Achaean enrichment event resulting in elevated U/Pb, Rb/Sr ratios and enrichment in LREEs. This source underwent a more recent fractionation, in the last 500 Myr that may have been related to the diamond-forming event. There is a strong correspondence between fluids with relatively unradiogenic Sr isotopes and relatively low (La, Nd, Sm)/(Nb, Zr) and (Ba, Th)/(Nb) ratios. Sr isotopic enrichment is accompanied by an increase in these ratios. The least trace element enriched and most isotopically depleted fluids are from the high-Mg carbonatitic suite. Thus, HDFs could be derived from asthenospheric mantle as low degree melts that interact to varying degrees with an ancient, metasomatized, rutile- and phlogopite bearing, sub continental lithosphere mantle. The internal heterogeneity in the Sr isotopic ratios within a single diamond suite and even within single diamonds may indicate fluid-mixing processes. Such mixing may occur during migration through preferred mantle veins and may be affected by the small-scale geochemical variability within them.

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

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

Rapid measurement of plasma free fatty acid concentration and isotopic enrichment using LC/MS

PubMed Central

Persson, Xuan-Mai T.; Błachnio-Zabielska, Agnieszka Urszula; Jensen, Michael D.

2010-01-01

Measurements of plasma free fatty acids (FFA) concentration and isotopic enrichment are commonly used to evaluate FFA metabolism. Until now, gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) was the best method to measure isotopic enrichment in the methyl derivatives of 13C-labeled fatty acids. Although IRMS is excellent for analyzing enrichment, it requires time-consuming derivatization steps and is not optimal for measuring FFA concentrations. We developed a new, rapid, and reliable method for simultaneous quantification of 13C-labeled fatty acids in plasma using high-performance liquid chromatography-mass spectrometry (HPLC/MS). This method involves a very quick Dole extraction procedure and direct injection of the samples on the HPLC system. After chromatographic separation, the samples are directed to the mass spectrometer for electrospray ionization (ESI) and analysis in the negative mode using single ion monitoring. By employing equipment with two columns connected parallel to a mass spectrometer, we can double the throughput to the mass spectrometer, reducing the analysis time per sample to 5 min. Palmitate flux measured using this approach agreed well with the GC/C/IRMS method. This HPLC/MS method provides accurate and precise measures of FFA concentration and enrichment. PMID:20526002

Specific pathways for the incorporation of dissolved barium and molybdenum into the bivalve shell: an isotopic tracer approach in the juvenile Great Scallop (Pecten maximus).

PubMed

Tabouret, Hélène; Pomerleau, Sébastien; Jolivet, Aurélie; Pécheyran, Christophe; Riso, Ricardo; Thébault, Julien; Chauvaud, Laurent; Amouroux, David

2012-07-01

Dissolved barium and molybdenum incorporation in the calcite shell was investigated in the Great Scallop Pecten maximus. Sixty six individuals were exposed for 16 days to two successive dissolved Ba and Mo concentrations accurately differentiated by two different isotopic enrichments (⁹⁷Mo, ⁹⁵Mo; ¹³⁵Ba, ¹³⁷Ba). Soft tissue and shell isotopic composition were determined respectively by quantitative ICP-MS (Inductively Coupled Plasma Mass Spectrometer) and laser ablation--ICP-MS. Results from Ba enrichment indicate the direct incorporation of dissolved Ba into the shell in proportion to the levels in the water in which they grew with a 6-8 day delay. The low spike contributions and the low partition coefficient (D(Mo) = 0.0049 ± 0.0013), show that neither the soft tissue nor the shell were significantly sensitive to Mo enrichment. These results eliminate direct Mo shell enrichment by the dissolved phase, and favour a trophic uptake that will be investigated using the successive isotopic enrichment approach developed in this study. Copyright © 2012 Elsevier Ltd. All rights reserved.

Process for preparing a chemical compound enriched in isotope content. [nitrogen 15-enriched nitric acid

DOEpatents

Michaels, E.D.

1981-02-25

A process to prepare a chemical enriched in isotope content includes: a chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products. A particular embodiment of the process in the production of nitrogen-15-enriched nitric acid.

Long-term enrichment of the stable isotopic composition of stream water due to the release of groundwater recharge from extreme precipitation events

NASA Astrophysics Data System (ADS)

Boutt, D. F.

2017-12-01

The isotopic composition of surface and groundwater is impacted by a multitude of hydrologic processes. The long-term response of these systems to hydrologic change is critical for appropriately interpreting isotopic information for streamflow generation, stream-aquifer-coupling, sources of water to wells, and understanding recharge processes. To evaluate the response time of stream-aquifer systems to extreme precipitation events we use a long-term isotope dataset from Western Massachusetts with drainage areas ranging from 0.1 to > 800 km2. The year of 2011 was the wettest calendar year on record and the months of August and September of 2011 were the wettest consecutive two-month period in the 123 year record. Stable isotopic composition of surface waters of catchments ranging from 1 - 1000 km2 show an enrichment due to summertime and Tropical Storm precipitation. Enrichment in potential recharge water is shown to have a significant long-term impact (> 3 hydrologic years) on the isotopic composition of both surface and groundwater. This highlights the importance of groundwater sources of baseflow to streams and the transient storage and release mechanisms of shallow groundwater storage. The length of isotopic recession of stream water are also a strong function of watershed area. It is concluded that the stream water isotopes are consistent with a large pulse of water being stored and released from enriched groundwater emplaced during this period of above-average precipitation. Ultimately the results point to the importance of considering hydrological processes of streamflow generation and their role in hydrologic processes beyond traditional catchment response analysis.

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

PubMed

Yurimoto, H; Ito, M; Nagasawa, H

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

PubMed

Yurimoto; Ito; Nagasawa

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Device and method for separating oxygen isotopes

DOEpatents

Rockwood, Stephen D.; Sander, Robert K.

1984-01-01

A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

Heterogeneity and O-16-Enrichments in Oxygen Isotope Ratios of Olivine from Chondrules in the Mokoia CV3 Chondrite

NASA Technical Reports Server (NTRS)

Jones, R. H.; Leshin, L. A.; Guan, Y.

2002-01-01

Two chondrules from Mokoia contain olivine in which oxygen isotopes are extremely heterogeneous, with some grains highly enriched in O-16. These data provide an important link between CAIs and chondrules. Additional information is contained in the original extended abstract.

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

PubMed

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

2014-08-19

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

Determination of phenylalanine isotope ratio enrichment by liquid chromatography/time- of-flight mass spectrometry.

PubMed

Wu, Zhanpin; Zhang, Xiao-Jun; Cody, Robert B; Wolfe, Robert R

2004-01-01

The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications.

Daily Variation of Heavy Carbon Dioxide in Mars Atmosphere

NASA Astrophysics Data System (ADS)

Livengood, T. A.; Kostiuk, Th; Kolasinski, J.; Hewagama, T.; Henning, W. G.; Sornig, M.; Stangier, T.; Krause, P.; Sonnabend, G.

2015-10-01

The atmosphere of Mars is significantly enriched in C and O heavy isotopes, detected by ground based high-resolution infrared spectroscopy as well as in situ measurements by the Phoenix lander and Mars Science Laboratory Curiosity rover. Heavy isotope enrichment is consistent with the preferential loss of light isotopes in eroding Mars' primordial atmosphere. Infrared spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF resolves rovibrational transitions of normal-isotope carbon dioxide as well as singly-substituted minor isotopologues, enabling remote measurements of carbon and oxygen isotope ratios as a function of latitude and local time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with contemporary in situ measurements by the Curiosity rover to investigate the degree of agreement between in situ and remote methods and potentially to calibrate the spectroscopic constants required to accurately evaluate isotope ratios all over Mars.

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2016-12-01

The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

Lie-Santilli isoapproach to the unification of gravity and electromagnetism

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

Animalu, A.O.E.

1996-06-01

The author reviews the problem of Einstein`s original proposal for the unification of gravity and electromagnetism in space-time differential geometry along the lines of the recent contributions by A.A. Logunov, R.M. Santilli, D.F. Lopez and others. The author presents a new method of unification based on the Lie-Santilli isotopic theory whereby the unified field tensor g = (g{sub {mu}{nu}}) is constructed from the symmetric Riemannian gravitational tensor, g = (g{mu}{nu}), and the antisymmetric electromagnetic field tensor F = (F{sub {mu}{nu}}) via an isotopic lifting g {yields} {cflx g} = Fg of the type of Lax pairing, where det F {ne}more » 0, the unified field {cflx g} satisfies Logunov-Santilli equations while g and F are treated as Lax pair. Because of Santilli`s isotopic equivalence between Minkowskian and Riemannian geometries, the author infers that in the Minkowskian limit F = f, g = {eta}, the metric {eta} satisfies Lax`s equation of motion {partial_derivative}{eta}/{partial_derivative}t = f{eta} {minus} {eta}f which insures the conservation of the eigenvalues of g. The invariance of the electromagnetic group of transformations (F) in Minkowski space is determined by the eigenvalue equations, det (F{sub {mu}{nu}}){minus}{lambda}{eta}{sub {mu}{nu}} = 0, from which the author deduces a Lie-isotopic {open_quotes}extended{close_quotes} relativity principle. A wave equation for a spin-2 particle in the unified field is derived, and the experimental consequences of the theory are discussed.« less

Hydrogen isotope separation utilizing bulk getters

DOEpatents

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

1991-08-20

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

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1991-01-01

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

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1990-01-01

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

Transgenerational marking of freshwater fishes with enriched stable isotopes: a tool for fisheries management and research.

PubMed

Munro, A R; Gillanders, B M; Thurstan, S; Crook, D A; Sanger, A C

2009-08-01

A promising new method of marking larval freshwater fishes with enriched stable isotopes by means of injecting the maternal parent with the marking agent was investigated. The (138)Ba:(137)Ba ratios in the otoliths of larval golden perch Macquaria ambigua were compared to determine the effect of injecting female broodstock with different dosages of enriched (137)Ba at various times before spawning. There was 100% mark success in the progeny of fish injected with 20 microg g(-1) of enriched (137)Ba 24 h before inducing spawning with hormones and 40 microg g(-1) administered at the same time as inducement of spawning. Injection of 40 microg g(-1) enriched (137)Ba 21 days before spawning resulted in only 81% mark success and suggests rapid elimination of barium in M. ambigua. Injection with enriched (137)Ba did not significantly affect the fertilization rate, number of fertilized eggs or hatching rate compared with long-term hatchery records. These results suggest that transgenerational marking is an effective and affordable means of mass-marking larval fishes. Thousands of larval fishes can be permanently marked with a unique artificial isotopic mark via a single injection into the maternal parent, thus avoiding the handling of individual fishes or having to deal with chemical baths. Because no single mark or tagging method is suitable for all situations, transgenerational marking with enriched stable isotopes provides another method for researchers and managers to discriminate both hatchery-reared and wild fishes.

A status of progress for the Laser Isotope Separation (LIS) process

NASA Technical Reports Server (NTRS)

Delionback, L. M.

1976-01-01

An overview of the Laser Isotope Separation (LIS) methodology is given together with illustrations showing a simplified version of the LIS technique, an example of the two-photon photoionization category, and a diagram depicting how the energy levels of various isotope influence the LIS process. Applications were proposed for the LIS system which, in addition to enriching uranium, could in themselves develop into programs of tremendous scope and breadth. These include the treatment of radioactive wastes from light-water nuclear reactors, enriching the deuterium isotope to make heavy-water, and enriching the light isotopes of such elements as titanium for aerospace weight-reducing programs. Economic comparisons of the LIS methodology with the current method of gaseous diffusion indicate an overwhelming advantage; the laser process promises to be 1000 times more efficient. The technique could also be utilized in chemical reactions with the tuned laser serving as a universal catalyst to determine the speed and direction of a chemical reaction.

Physics overview of AVLIS

NASA Astrophysics Data System (ADS)

Solarz, R. W.

1985-02-01

Atomic vapor laster isotope separation (AVLIS) represents the largest-scale potential application of tunable lasers that has received serious attention. The underlying physical principles were identified and optimized, the major technology components were developed, and the integrated enrichment performance of the process was tested. The central physical processes are outlined, progress to date on the technology elements is reviewed, and scaling laws are fomulated. Two primary applications are the production of light-water reactor fuel and the conversion of fuel-grade plutonium to weapons-grade material. A variety of applications exist that all potentially use a common base of AVLIS technology. These include missions such as the enrichment of mercury isotopes to improve fluorescent lamp efficiency, the enrichment of iodine isotopes for medical isotope use, and the cleanup of strontium from defense waste for recovering strontium isotopes for radiothermal mechanical generators. The ability to radidly assess the economic and technical feasibility of each mission is derived from the general applicability of AVLIS physics and AVLIS technology.

Isotopic compositions of cometary matter returned by Stardust.

PubMed

McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

2006-12-15

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

Target-fueled nuclear reactor for medical isotope production

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

Coats, Richard L.; Parma, Edward J.

A small, low-enriched, passively safe, low-power nuclear reactor comprises a core of target and fuel pins that can be processed to produce the medical isotope .sup.99Mo and other fission product isotopes. The fuel for the reactor and the targets for the .sup.99Mo production are the same. The fuel can be low enriched uranium oxide, enriched to less than 20% .sup.235U. The reactor power level can be 1 to 2 MW. The reactor is passively safe and maintains negative reactivity coefficients. The total radionuclide inventory in the reactor core is minimized since the fuel/target pins are removed and processed after 7more » to 21 days.« less

Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

NASA Astrophysics Data System (ADS)

Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

2018-05-01

Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of redox processes in the mantle.

Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

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

Pearson, Scott, F.; Levey, Douglas, J.; Greenberg, Catheryn, H.

2003-02-28

Pearson, S.F., D.J. Levey, C.H. Greenberg, and C.M. del Rio. 2003. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird. Oecologia. 135:516-523. The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped warblers (Dendroica coronata) to determine d15N and d13C turnover rates for blood, d15N and d13C diet-tissue discrimination factors, andmore » diet-tissue relationships for blood and feathers. After 3 weeks on a common diet, 36 warblers were assigned to one of four diets differing in the relative proportion of fruit and insects. Plasma half-life estimates ranged from 0.4 to 0.7 days for d13C and from 0.5 to 1.7 days for d15N. Half-life did not differ among diets. Whole blood half-life for d13C ranged from 3.9 to 6.1 days. Yellow-rumped warbler tissues were enriched relative to diet by 1.7.3.6% for nitrogen isotopes and by 1.2 to 4.3% for carbon isotopes, depending on tissue and diet. Consistent with previous studies, feathers were the most enriched and whole blood and plasma were the least enriched or, in the case of carbon, slightly depleted relative to diet. In general, tissues were more enriched relative to diet for birds with high percentages of insects. For all tissues, carbon and nitrogen isotope discrimination factors increased with carbon and nitrogen concentrations of diets. The isotopic signature of plasma increased linearly with the sum of the isotopic signature of the diet and the discrimination factor. Because the isotopic signature of tissues depends on both elemental concentration and isotopic signature of the diet, attempts to reconstruct diet from stable isotope signatures require mixing models that incorporate elemental concentration.« less

Gold and isotopically enriched platinium targets for the production of radioactive beams of francium

NASA Astrophysics Data System (ADS)

Lipski, A. R.; Orozco, L. A.; Pearson, M. R.; Simsarian, J. E.; Sprouse, G. D.; Zhao, W. Z.

1999-12-01

Au and isotopically enriched Pt targets are discussed for the production of radioactive Fr beams. Target foils, serving also as ionizers, have to be heated in order to enhance the diffusion of atoms to the surface for further extraction and injection into the electrostatic transport system.

Accurate isotopic fission yields of electromagnetically induced fission of 238U measured in inverse kinematics at relativistic energies

NASA Astrophysics Data System (ADS)

Pellereau, E.; Taïeb, J.; Chatillon, A.; Alvarez-Pol, H.; Audouin, L.; Ayyad, Y.; Bélier, G.; Benlliure, J.; Boutoux, G.; Caamaño, M.; Casarejos, E.; Cortina-Gil, D.; Ebran, A.; Farget, F.; Fernández-Domínguez, B.; Gorbinet, T.; Grente, L.; Heinz, A.; Johansson, H.; Jurado, B.; Kelić-Heil, A.; Kurz, N.; Laurent, B.; Martin, J.-F.; Nociforo, C.; Paradela, C.; Pietri, S.; Rodríguez-Sánchez, J. L.; Schmidt, K.-H.; Simon, H.; Tassan-Got, L.; Vargas, J.; Voss, B.; Weick, H.

2017-05-01

SOFIA (Studies On Fission with Aladin) is a novel experimental program, dedicated to accurate measurements of fission-fragment isotopic yields. The setup allows us to fully identify, in nuclear charge and mass, both fission fragments in coincidence for the whole fission-fragment range. It was installed at the GSI facility (Darmstadt), to benefit from the relativistic heavy-ion beams available there, and thus to use inverse kinematics. This paper reports on fission yields obtained in electromagnetically induced fission of 238U.

A new feature in the internal heavy isotope distribution in ozone.

PubMed

Bhattacharya, S K; Savarino, Joel; Michalski, G; Liang, Mao-Chang

2014-10-07

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ((18)O/(16)O and (17)O/(16)O ratio) which does not follow normal mass fractionation rule: δ(17)O ∼ 0.52(*)δ(18)O, expressed as an anomaly Δ(17)O = δ(17)O - 0.52(*)δ(18)O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ(18)O (s) or δ(18)O (as) (and similarly for δ(17)O) as well as position dependent isotope anomaly Δ(17)O (s) and Δ(17)O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ(17)O (s) is zero. Consequently, Δ(17)O (as) = 1.5 (*) Δ(17)O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

A new feature in the internal heavy isotope distribution in ozone

NASA Astrophysics Data System (ADS)

Bhattacharya, S. K.; Savarino, Joel; Michalski, G.; Liang, Mao-Chang

2014-10-01

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition (18O/16O and 17O/16O ratio) which does not follow normal mass fractionation rule: δ17O ˜ 0.52*δ18O, expressed as an anomaly Δ17O = δ17O - 0.52*δ18O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ18O (s) or δ18O (as) (and similarly for δ17O) as well as position dependent isotope anomaly Δ17O (s) and Δ17O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ17O (s) is zero. Consequently, Δ17O (as) = 1.5 * Δ17O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

Isotopic effects on phonon anharmonicity in layered van der Waals crystals: Isotopically pure hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Cuscó, Ramon; Artús, Luis; Edgar, James H.; Liu, Song; Cassabois, Guillaume; Gil, Bernard

2018-04-01

Hexagonal boron nitride (h -BN) is a layered crystal that is attracting a great deal of attention as a promising material for nanophotonic applications. The strong optical anisotropy of this crystal is key to exploit polaritonic modes for manipulating light-matter interactions in 2D materials. h -BN has also great potential for solid-state neutron detection and neutron imaging devices, given the exceptionally high thermal neutron capture cross section of the boron-10 isotope. A good knowledge of phonons in layered crystals is essential for harnessing long-lived phonon-polariton modes for nanophotonic applications and may prove valuable for developing solid-state 10BN neutron detectors with improved device architectures and higher detection efficiencies. Although phonons in graphene and isoelectronic materials with a similar hexagonal layer structure have been studied, the effect of isotopic substitution on the phonons of such lamellar compounds has not been addressed yet. Here we present a Raman scattering study of the in-plane high-energy Raman active mode on isotopically enriched single-crystal h -BN. Phonon frequency and lifetime are measured in the 80-600-K temperature range for 10B-enriched, 11B-enriched, and natural composition high quality crystals. Their temperature dependence is explained in the light of perturbation theory calculations of the phonon self-energy. The effects of crystal anisotropy, isotopic disorder, and anharmonic phonon-decay channels are investigated in detail. The isotopic-induced changes in the phonon density of states are shown to enhance three-phonon anharmonic decay channels in 10B-enriched crystals, opening the possibility of isotope tuning of the anharmonic phonon decay processes.

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

NASA Astrophysics Data System (ADS)

Kato, Chizu; Moynier, Frédéric

2017-12-01

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

Leaf water enrichment of stable water isotopes (δ18O and δD) in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Tjoa, Aiyen; Knohl, Alexander

2017-04-01

During the last few decades, Indonesia experienced rapid and large scale land-use change towards intensively managed crops, one of them is oil palm. This transition results in warmer and dryer conditions in microclimate. The impacts on the hydrological cycle and on water-use by plants are, however, not yet completely clear. Water stable isotopes are useful tracers of the hydrological processes and can provide means to partition evapotranspiration into evaporation and transpiration. A key parameter, however, is the enrichment of water stable isotope in plant tissue such as leaves that can provide estimates on the isotopic composition of transpiration. Here we present the results of a field campaign conducted in a mature oil palm plantation in Jambi province, Indonesia. We combined continuous measurements of water vapor isotopic composition and mixing ratio with isotopic analysis of water stored in different pools like oil palm leaves, epiphytes, trunk organic matter and soil collected over a three days period. Leaf enrichment varied from -2 ‰ to 10 ‰ relative to source (ground) water. The temporal variability followed Craig and Gordon model predictions for leaf water enrichment. An improved agreement was reached after considering the Péclet effect with an appropriate value of the characteristic length (L). Measured stomatal conductance (gs) on two different sets of leaves (top and bottom canopy) was mainly controlled by radiation (photosynthetically active radiation) and vapor pressure deficit. We assume that this control could be explained in conditions where soil water content is not representing a limiting factor. Understanding leaf water enrichment provides one step towards partitioning ET.

99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

PubMed

Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

2018-03-01

99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2014-09-10

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, probably the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs while processes within leaves or during phloem loading may contribute to the overall autotrophic – heterotrophic difference in carbon isotope compositions.« less

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

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

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

1989-12-01

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

Dispersal of adult culex mosquitoes in an urban west nile virus hotspot: a mark-capture study incorporating stable isotope enrichment of natural larval habitats.

PubMed

Hamer, Gabriel L; Anderson, Tavis K; Donovan, Danielle J; Brawn, Jeffrey D; Krebs, Bethany L; Gardner, Allison M; Ruiz, Marilyn O; Brown, William M; Kitron, Uriel D; Newman, Christina M; Goldberg, Tony L; Walker, Edward D

2014-03-01

Dispersal is a critical life history behavior for mosquitoes and is important for the spread of mosquito-borne disease. We implemented the first stable isotope mark-capture study to measure mosquito dispersal, focusing on Culex pipiens in southwest suburban Chicago, Illinois, a hotspot of West Nile virus (WNV) transmission. We enriched nine catch basins in 2010 and 2011 with 15N-potassium nitrate and detected dispersal of enriched adult females emerging from these catch basins using CDC light and gravid traps to distances as far as 3 km. We detected 12 isotopically enriched pools of mosquitoes out of 2,442 tested during the two years and calculated a mean dispersal distance of 1.15 km and maximum flight range of 2.48 km. According to a logistic distribution function, 90% of the female Culex mosquitoes stayed within 3 km of their larval habitat, which corresponds with the distance-limited genetic variation of WNV observed in this study region. This study provides new insights on the dispersal of the most important vector of WNV in the eastern United States and demonstrates the utility of stable isotope enrichment for studying the biology of mosquitoes in other disease systems.

Collisionless dissociation and isotopic enrichment of SF6 using high-powered CO2 laser radiation

NASA Technical Reports Server (NTRS)

Gower, M. C.; Billman, K. W.

1977-01-01

Dissociation of S-32F6 and the resultant isotopic enrichment of S-34F6 using high-powered CO2 laser radiation has been studied with higher experimental sensitivity than previously reported. Enrichment factors have been measured as a function of laser pulse number, wavelength, energy and time duration. A geometry independent dissociation cross section is introduced and measured values are presented. Threshold energy densities, below which no dissociation was observed, were also determined.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Determination of 13C isotopic enrichment of valine and threonine by GC-C-IRMS after formation of the N(O,S)-ethoxycarbonyl ethyl ester derivatives of the amino acids.

PubMed

Godin, Jean-Philippe; Faure, Magali; Breuille, Denis; Hopfgartner, Gérard; Fay, Laurent-Bernard

2007-06-01

We describe a new method of assessing, in a single run, (13)C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ((13)C-valine or (13)C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low (13)C isotopic enrichment. For inter-day repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32 per thousand. The (13)C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n = 4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

Isotope effects accompanying evaporation of water from leaky containers.

PubMed

Rozanski, Kazimierz; Chmura, Lukasz

2008-03-01

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

The origin of volatile element depletion in early solar system material: Clues from Zn isotopes in chondrules

NASA Astrophysics Data System (ADS)

Pringle, Emily A.; Moynier, Frédéric; Beck, Pierre; Paniello, Randal; Hezel, Dominik C.

2017-06-01

Volatile lithophile elements are depleted in the different planetary materials to various degrees, but the origin of these depletions is still debated. Stable isotopes of moderately volatile elements such as Zn can be used to understand the origin of volatile element depletions. Samples with significant volatile element depletions, including the Moon and terrestrial tektites, display heavy Zn isotope compositions (i.e. enrichment of 66Zn vs. 64Zn), consistent with kinetic Zn isotope fractionation during evaporation. However, Luck et al. (2005) found a negative correlation between δ66Zn and 1/[Zn] between CI, CM, CO, and CV chondrites, opposite to what would be expected if evaporation caused the Zn abundance variations among chondrite groups. We have analyzed the Zn isotope composition of multiple samples of the major carbonaceous chondrite classes: CI (1), CM (4), CV (2), CO (4), CB (2), CH (2), CK (4), and CK/CR (1). The bulk chondrites define a negative correlation in a plot of δ66Zn vs 1/[Zn], confirming earlier results that Zn abundance variations among carbonaceous chondrites cannot be explained by evaporation. Exceptions are CB and CH chondrites, which display Zn systematics consistent with a collisional formation mechanism that created enrichment in heavy Zn isotopes relative to the trend defined by CI-CK. We further report Zn isotope analyses of chondrite components, including chondrules from Allende (CV3) and Mokoia (CV3), as well as an aliquot of Allende matrix. All chondrules are enriched in light Zn isotopes (∼500 ppm on 66Zn/64Zn) relative to the bulk, contrary to what would be expected if Zn were depleted during evaporation, on the other hand the matrix has a complementary heavy isotope composition. We report sequential leaching experiments in un-equilibrated ordinary chondrites, which show sulfides are isotopically heavy compared to silicates and the bulk meteorite by ca. +0.65 per mil on 66Zn/64Zn. We suggest isotopically heavy sulfides were removed from either chondrules or their precursors, thereby producing the light Zn isotope enrichments in chondrules.

Heavy atom labeled nucleotides for measurement of kinetic isotope effects.

PubMed

Weissman, Benjamin P; Li, Nan-Sheng; York, Darrin; Harris, Michael; Piccirilli, Joseph A

2015-11-01

Experimental analysis of kinetic isotope effects represents an extremely powerful approach for gaining information about the transition state structure of complex reactions not available through other methodologies. The implementation of this approach to the study of nucleic acid chemistry requires the synthesis of nucleobases and nucleotides enriched for heavy isotopes at specific positions. In this review, we highlight current approaches to the synthesis of nucleic acids enriched site specifically for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Direct analysis of δ2H and δ18O in natural and enriched human urine using laser-based, Off-Axis Integrated Cavity Output Spectroscopy

PubMed Central

Berman, Elena S.F.; Fortsona, Susan L.; Snaith, Steven P.; Gupta, Manish; Baer, Douglas S.; Chery, Isabelle; Blanc, Stephane; Melanson, Edward L.; Thomson, Peter J; Speakman, John R.

2012-01-01

The stable isotopes of hydrogen (δ2H) and oxygen (δ18O) in human urine are measured during studies of total energy expenditure by the doubly labeled water method, measurement of total body water, and measurement of insulin resistance by glucose disposal among other applications. An ultrasensitive laser absorption spectrometer based on off-axis integrated cavity output spectroscopy was demonstrated for simple and inexpensive measurement of stable isotopes in natural isotopic abundance and isotopically enriched human urine. Preparation of urine for analysis was simple and rapid (approx. 25 samples per hour), requiring no decolorizing or distillation steps. Analysis schemes were demonstrated to address sample-to-sample memory while still allowing analysis of 45 natural or 30 enriched urine samples per day. The instrument was linear over a wide range of water isotopes (δ2H = −454 to +1702 ‰ and δ18O= −58.3 to +265 ‰). Measurements of human urine were precise to better than 0.65 ‰ 1σ for δ2H and 0.09 ‰ 1σ for δ18O for natural urines, 1.1 ‰ 1σ for δ2H and 0.13 ‰ 1σ for δ18O for low enriched urines, and 1.0 ‰ 1σ for δ2H and 0.08 ‰ 1σ for δ18O for high enriched urines. Furthermore, the accuracy of the isotope measurements of human urines was verified to better than ±0.81 ‰ in δ2H and ±0.13 ‰ in δ18O (average deviation) against three independent IRMS laboratories. The ability to immediately and inexpensively measure the stable isotopes of water in human urine is expected to increase the number and variety of experiments which can be undertaken. PMID:23075099

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

Investigation of isotope effects of ozone as a function of temperature

NASA Astrophysics Data System (ADS)

McMahon, Daniel J.

Ozone is an important oxidizer in the atmosphere and plays a crucial role as a cleanser, removing various compounds such NOx and SOx. It also is intriguing to those that study stable isotopes as it has a unique signature found in no other oxygen containing molecule. Ozone is observed to fractionate mass independently, which means it does not follow the typical delta 17O /delta18O = 0.52 ratio expected for molecules enriched with 17O and 18O. The magnitude of ozone's mass independent enrichment has been studied in laboratory experiments and atmospheric observations but its explanation is still incomplete. Symmetry of the isotopically substituted ozone is postulated to be the source of mass independent enrichment and this thesis will build on that explanation to examine the magnitude of isotopic enrichment as a function of temperature. Understanding of the kinetics of ozone formation has come a long way from early predictions of enrichments >200‰ However, while our ability to accurately model ozone's bulk isotopic enrichment has improved to include separate rates for the formation of asymmetric and symmetric ozone, rate experiments are sparse for 17O and of low precision. To improve our understanding of ozone's enrichment, this study presents a temperature dependent enrichment experiment and series of models to predict asymmetric mass independent fractionation. This also served to examine ozone's enrichment in the troposphere by using an open flow experimental setup which is in contrast to previous works examining ozone enrichment in a closed system. Our experimental observations show that under tropospheric conditions, ozone should have delta17O ≈ 75‰, delta18O ≈ 80‰, and delta 17O ≈ 33‰. The models were able to match experimental values, often within 1‰, and with minimal assumptions, predict asymmetric ozone to have delta17O=47.5‰. This value is important as ozone transfers its terminal atom to species it oxidizes and will be the starting point to using ozone as a tracer in atmospheric reactions. Modeling improves our understanding of ozone's enrichments but these predictions must be validated by atmospheric observations. Previous tropospheric ozone sampling studies produced data of low precision but still showed relatively good agreement with our laboratory observations. In order to obtain better isotopic data a proxy method for sampling ozone's terminal atom is needed. Reaction with nitrite in solution is promising as the reaction is rapid and efficient. However we were unable to obtain tropospheric ozone observations as nitrite processing methods could not be perfected to remove nitrate blank concentrations. We do present the merits of using nitrite to react with atmospheric ozone and the suggest purification steps that may allow this method to be successful in the future.

75 FR 42466 - Notice of Availability of Draft Environmental Impact Statement and Public Meeting for the AREVA...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-21

... electrical transmission line required to power the proposed EREF. On March 17, 2010, the NRC granted an... facility. Specifically, AES proposes to use gas centrifuge technology to enrich the uranium-235 isotope... centrifuge-based technology to enrich the uranium- 235 isotope found in natural uranium to concentrations up...

Influence of uncertainties of isotopic composition of the reprocessed uranium on effectiveness of its enrichment in gas centrifuge cascades

NASA Astrophysics Data System (ADS)

Smirnov, A. Yu; Mustafin, A. R.; Nevinitsa, V. A.; Sulaberidze, G. A.; Dudnikov, A. A.; Gusev, V. E.

2017-01-01

The effect of the uncertainties of the isotopic composition of the reprocessed uranium on its enrichment process in gas centrifuge cascades while diluting it by adding low-enriched uranium (LEU) and waste uranium. It is shown that changing the content of 232U and 236U isotopes in the initial reprocessed uranium within 15% (rel.) can significantly change natural uranium consumption and separative work (up to 2-3%). However, even in case of increase of these parameters is possible to find the ratio of diluents, where the cascade with three feed flows (depleted uranium, LEU and reprocessed uranium) will be more effective than ordinary separation cascade with one feed point for producing LEU from natural uranium.

Estimating wetland connectivity to streams in the Prairie Pothole Region: An isotopic and remote sensing approach

USGS Publications Warehouse

Brooks, J. R.; Mushet, David M.; Vanderhoof, Melanie; Leibowitz, Scott G.; Neff, Brian; Christensen, J. R.; Rosenberry, Donald O.; Rugh, W. D.; Alexander, L.C.

2018-01-01

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding the reliance of stream flow on inputs from wetlands. We used the isotopic evaporation signal in water and remote sensing to examine wetland‐stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie‐pothole wetlands. Pipestem Creek exhibited an evaporated‐water signal that had approximately half the isotopic‐enrichment signal found in most evaporatively enriched prairie‐pothole wetlands. Groundwater adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment, indicating that enriched surface water did not contribute significantly to groundwater discharging into Pipestem Creek. The estimated surface water area necessary to generate the evaporation signal within Pipestem Creek was highly dynamic, varied primarily with the amount of discharge, and was typically greater than the immediate Pipestem Creek surface water area, indicating that surficial flow from wetlands contributed to stream flow throughout the summer. We propose a dynamic range of spilling thresholds for prairie‐pothole wetlands across the watershed allowing for wetland inputs even during low‐flow periods. Combining Landsat estimates with the isotopic approach allowed determination of potential (Landsat) and actual (isotope) contributing areas in wetland‐dominated systems. This combined approach can give insights into the changes in location and magnitude of surface water and groundwater pathways over time. This approach can be used in other areas where evaporation from wetlands results in a sufficient evaporative isotopic signal.

Isotope pattern deconvolution as a tool to study iron metabolism in plants.

PubMed

Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio; Lucena, Juan José; García-Tomé, Maria Luisa; Hernández-Apaolaza, Lourdes

2008-01-01

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.

Mass-dependent and -independent fractionation of Fe isotopes in magnetotactic bacteria

NASA Astrophysics Data System (ADS)

Amor, M.; Busigny, V.; Louvat, P.; Gelabert, A.; Cartigny, P.; Durand-Dubief, M.; Ona-Nguema, G.; Alphandéry, E.; Chebbi, I.; Guyot, F. J.

2016-12-01

Magnetotactic bacteria (MTB) perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the oldest microorganisms capable of biomineralization on Earth, identification of their activity in the geological record remains poorly resolved because of the lack of reliable signatures. Here, we determined Fe isotope fractionation by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1 to better understand Fe cycling in MTB and provide new signatures of the contribution of MTB to iron geochemistry. AMB-1 strain was cultivated with either Fe(III)-quinate or Fe(II)-ascorbate as Fe sources. Iron isotope composition of Fe sources, bacterial growth media after AMB-1 cultures, bacterial lysates (corresponding to AMB-1 cells devoid of magnetite) and magnetite samples were analyzed by MC-ICP-MS after column chromatography. In the two culture conditions, growth media after AMB-1 cultures were enriched in light Fe isotopes relative to Fe sources. Two distinct bacterial Fe reservoirs were characterized in AMB-1: (1) magnetite enriched in the light Fe isotopes by 1.5 to 2.5‰ in δ56Fe relative to Fe sources, and (2) lysate enriched in the heavy Fe isotopes by 0.3 to 0.8‰ relative to Fe sources. More importantly, mass-independent fractionations in odd (57Fe) but not in even isotopes (54Fe, 56Fe and 58Fe) were observed for the first time, highlighting a magnetic isotope effect. Magnetite samples were significantly enriched in 57Fe by 0.23‰ relative to 54Fe, 56Fe and 58Fe. Based on our results, we propose a model for Fe cycling and magnetite biomineralization in AMB-1, and propose to use this specific mass-independent signature of Fe isotopes to evaluate the contribution of MTB to the iron biogeochemistry of recent and ancient environmental samples.

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Dworkin, Jason P.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Midcontinent rift volcanism in the Lake Superior region: Sr, Nd, and Pb isotopic evidence for a mantle plume origin

USGS Publications Warehouse

Nicholson, S.W.; Shirey, S.B.

1990-01-01

Between 1091 and 1098 Ma, most of a 15- to 20-km thickness of dominantly tholeiitic basalt erupted in the Midcontinent Rift System of the Lake Superior region, North America. The Portage Lake Volcanics in Michigan, which are the younget MRS flood basalts, fall into distinctly high- and low-TiO2 types having different liquid lines of descent. Incompatible trace elements in both types of tholeiites are enriched compared to depleted or primitive mantle and both basalt types are isotopically indistinguishable. The isotopic enrichment of the MRS source compared to depleted mantle is striking and must have occurred at least 700 m.y. before 1100 Ma. There are two likely sources for such magmatism: subcontinental lithospheric mantle enriched during the early Proterozoic or enriched mantle derived from an upwelling plume. Decompression melting of an upwelling enriched mantle plume in a region of lithosphere thinned by extension could have successfully generated the enormous volume (850 ?? 103 km3) of relatively homogeneous magma in a restricted time interval. -from Authors

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

1994-01-01

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

Electromagnetic moments and electric dipole transitions in carbon isotopes

NASA Astrophysics Data System (ADS)

Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi

2003-07-01

We carry out shell model calculations to study electromagnetic moments and electric dipole transitions of C isotopes. We point out the configuration dependence of the quadrupole and magnetic moments of the odd C isotopes, which will be useful to find out the deformations and the spin parities of the ground states of these nuclei. We also study the electric dipole states of C isotopes, focusing on the interplay between low energy pigmy strength and giant dipole resonances. As far as the energies of the resonances are concerned, reasonable agreement is obtained with available experimental data for the photoreaction cross sections in 12C, 13C, and 14C, both in the low energy region below ħω=14 MeV and in the high energy giant resonance region (14 MeV <ħω⩽30 MeV). The calculated transition strength below the giant dipole resonance (ħω⩽14 MeV) in C isotopes heavier than 15C is found to exhaust about 12 16 % of the classical Thomas-Reiche-Kuhn sum rule value and 50 80 % of the cluster sum rule value.

Fast-Neutron Activation of Long-Lived Isotopes in Enriched Ge

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

Elliott, Steven R.; Guiseppe, Vincente; LaRoque, B. H.

2010-11-16

We measured the production of 57Co, 54Mn, 68Ge, 65Zn, and 60Co in an sample of Ge enriched in isotope 76 due to high-energy neutron interactions. These isotopes are critical in understanding background in Ge detectors used for double-beta decay experiments. These isotopes are produced by cosmogenic-neutron interactions in the detectors while they reside on the Earth's surface. We compared the measured production to that predicted by cross-section calculations based on CEM03.02. The cross section calculations over-predict our measurements by approximately a factor of 2-3 depending on isotope. We then use the measured cosmic-ray neutron ux and our results to predictmore » the cosmogenic production rate with an accuracy near 15%.« less

Carbon isotopic fractionation in heterotrophic microbial metabolism

NASA Technical Reports Server (NTRS)

Blair, N.; Leu, A.; Munoz, E.; Olsen, J.; Kwong, E.; Des Marais, D.

1985-01-01

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Carbon and nitrogen stable isotope analysis of three types of oyster tissue in an impacted estuary

NASA Astrophysics Data System (ADS)

Piola, Richard F.; Moore, Stephanie K.; Suthers, Iain M.

2006-01-01

The stable isotope ratios of carbon ( δ13C) and nitrogen ( δ15N) of the muscle, ctenidia and viscera of the Sydney rock oyster, Saccostrea glomerata, showed the dilution and assimilation of tertiary treated sewage along an estuarine gradient. The enriched 15N values of oyster ctenidia and viscera from within 50 m of the sewage outfall indicated the use of 15N-enriched tertiary treated sewage effluent (16 ± 2.3‰) as a nutrient source. The effect of sewage nitrogen on oyster δ15N was localised, with oysters 5 km upstream and downstream of the outfall not significantly enriched. Viscera δ15N was most sensitive to sewage nutrients and δ13C significantly defined an ocean-to-estuarine gradient. High variance in isotope ratios of viscera compromised its use as an indicator of anthropogenic nutrients, and this also reduced the utility of whole-body stable isotope ratios. Ctenidia was the most useful indicator tissue of sewage discharge at the scale of this study, being consistently and significantly enriched in δ15N close to the sewage outfall and δ13C clearly defined an estuarine gradient with less internal variability than viscera. Muscle δ15N was least sensitive to sewage effluent and showed the least variability, making it more suited to investigations of anthropogenic nutrient enrichment over larger spatio-temporal scales.

Origin of low δ26Mg basalts with EM-I component: Evidence for interaction between enriched lithosphere and carbonated asthenosphere

NASA Astrophysics Data System (ADS)

Tian, H.; Yang, W.; Li, S. G.; Ke, S.; Chu, Z. Y.

2016-12-01

Many studies have focused on the interactions between recycled materials and depleted mantle to explain the origins of EM and HIMU components (e.g., Cohen and O'Nions, 1982; White and Hofmann, 1982). However, little is known about the interactions between recycled materials and enriched mantle and the associated consequences, e.g., late recycled crustal material overprints mantle previously enriched by earlier recycling events of the crust. Recently, light Mg isotopic composition of the basalts from North China Craton (NCC) and South China Block (SCB) has been attributed to recycled carbonate metasomatism from subducted Pacific slab (Yang et al., 2012; Huang et al., 2015). If this explanation is correct, the Cenozoic basalts from Northeast (NE) China should also contain light Mg isotopic compositions. The basalts from NE China have EMI Sr-Nd-Pb isotopic features that are distinct from the NCC and SCB basalts, indicating the contribution of an enriched mantle source (Choi et al., 2006; Chu et al., 2013). Therefore, Mg isotopic compositions of the Cenozoic basalts from NE China will help to determine the interaction between recycled sedimentary carbonates and an enriched mantle. Consistent with the hypothesis, our results show that the Cenozoic basalts from Wudalianchi and Erkeshan, NE China, have homogeneous and light Mg isotopic compositions (δ26Mg =-0.57 to -0.46‰). Based on the similarity to the basalts from NCC and SCB, their light Mg isotopic feature should also be derived from carbonate metasomatism (i.e. carbonated asthenosphere). In addition to that, a question arise that why the interaction between carbonated asthenosphere and the EM-I SLCM significantly modify the trace element and Sr-Nd-Pb isotopic composition of the mantle-derived melt, but have little effect on the Mg isotopes? The possible mechanism is the interaction between low SiO2 melt and peridotite, which converts pyroxene to olivine, as reported in previous studies (e.g., Kelemen et al., 1992; Edwards and Malpas, 1996; Zhou et al., 1996, 2014). During the interaction, the trace elements of the EM-I SCLM largely entered the melt, and all Mg was transferred from Opx and Cpx into the newly formed olivine. Consequently, the Wudalianchi and Erkeshan basalts preserve low δ26Mg and obtain EM-I Sr-Nd-Pb isotopic compositions (Fig. 1).

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Experimental identification of mechanisms controlling calcium isotopic fractionations by the vegetation.

NASA Astrophysics Data System (ADS)

Cobert, Florian; Schimtt, Anne-Désirée.; Bourgeade, Pascale; Stille, Peter; Chabaux, François; Badot, Pierre-Marie; Jaegler, Thomas

2010-05-01

This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the co-occuring geochemical and physiological process and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 6 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered as infinite. A second experiment (non infinite L6) allowed Ca depletion in the solution through time; therefore, response effects on the Ca isotopic signatures in the plant organs and in the nutritive solution were observed. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Preliminary results show that: (1) the roots (main and secondary) were enriched in the light isotope (40Ca) compared to the nutritive solution, and leaves were enriched in the heavy isotope (44Ca) compared to stems. These results are in accord with previously published field studies (Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). Leaves and secondary roots were however enriched in the heavy isotope (44Ca) compared to bean pods, stems and main roots. These results could be related to kinetic fractionation processes occurring either during the Ca root uptake, or during the Ca transport within the plant, or physiological mechanisms occurring first at the level of secondary roots, and second at the level of leaves. (2) No Ca isotope difference was observed neither between old and young organs, (except for H6 leaves), nor between the two growth stages (except for H6 roots). This suggest that the mechanisms controlling isotopic fractionations of Ca within common beans do not vary during growth, and that the nutrients stored in the cotyledons have only a minor effect on the Ca isotope fractionations of plants harvested after 10 days. (3) Strongest Ca isotope fractionations were observed at the nutritive solution/root interface. This implies that the mechanisms of light isotope enrichments in the plant are mainly due to transport processes taking place at this interface. (4) The non infinite L6 nutritive solution became enriched in 44Ca during the experiment compared to the infinite L6 nutritive solution and all the other solutions (L4, H4, and H6). This enrichment can be explained by Rayleigh fractionation or isotopic equilibrium. (5) Bean organs, from L4 and non infinite L6 experiment conditions, were enriched in 44Ca compared to stems and roots cultivated under H4, H6 and infinite L6 conditions. This might be due to the limited Ca in the nutritive solutions that cause smallest Ca isotope fractionations in the bean organs. All these results show that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that physiological effects have also to be involved. They confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems.

COMPOUND-SPECIFIC CARBON AND HYDROGEN ISOTOPE ANALYSIS-FIELD EVIDENCE OF MTBE BIOREMEDIATION

EPA Science Inventory

Chemical reactions (including bio- and abiotic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting in enrichment of the heavier isotopic species (13C, D) in the unreacted substrate, referred to as isotopic fractionation. On the other ...

Effect of NO2(-) on stable isotope fractionation during bacterial sulfate reduction.

PubMed

Einsiedl, Florian

2009-01-01

The effects of low NO2(-) concentrations on stable isotope fractionation during dissimilatory sulfate reduction by strain Desulfovibrio desulfuricans were investigated. Nitrite, formed as an intermediate during nitrification and denitrification processes in marine and freshwater habitats, inhibits the reduction of the sulfuroxy intermediate SO3(2-) to H2S even at low concentrations. To gain an understanding of the inhibition effect of the reduction of the sulfuroxy intermediate on stable isotope fractionation in sulfur and oxygen during bacterial sulfate reduction, nitrite was added in the form of short pulses. In the batch experiments that contained 0.02, 0.05, and 0.1 mM nitrite, sulfur enrichment factors epsilon of -12 +/- 1.6, -15 +/- 1.1, and -26 +/- 1.3 per thousand, respectively were observed. In the control experiment (no addition of nitrite) a sulfur enrichment factor epsilon of around -11 per thousand was calculated. In the experiments that contained no 18O enriched water (delta18O: -10 per thousand) and nitrite concentrations of 0.02, 0.05, and 0.1 mM, delta18O values in the remaining sulfate were fairly constant during the experiments (delta18O sulfate: approximately equal to 10 per thousand) and were similar to those obtained from the control experiment (no nitrite and no enriched water). However, in the batch experiments that contained 18O enriched water (+700 per thousand) and nitrite concentrations of 0.05 and 0.1 mM increasing delta18O values in the remaining sulfate from around 15 per thousand to approximately 65 and 85 per thousand, respectively, were found. Our experiments that contained isotopic enriched water and nitrite show clear evidence that the ratio of forward and backward fluxes regulated by adenosine-5'-phosphosulfate reductase (APSR) controls the extent of sulfur isotope fractionation during bacterial sulfate reduction in strain Desulfovibrio desulfuricans. Since the metabolic sulfuroxy intermediate SO3(2-) exchanges with water, evidence of 18O enriched water in the remaining sulfate in the experiments that contained nitrite also demonstrates that SO3(2-) recycling to sulfate affects sulfur and oxygen isotope fractionation during bacterial sulfate reduction to some extent. Even though reduction of adenosine-5'-phosphosulfate (APS) to sulfite of -25 per thousand was not fully expressed, SO3(2-) was recycled to SO4(2-). On the basis of the results of this study a sulfur isotope fractionation for APSR of upto approximately -30 per thousand can be assumed. However, reported NO2(-) concentrations of up to 20 microM in freshwater and marine habitats may not significantly impact the ability to use stable isotope analysis in assessing bacterial sulfate reduction.

Using stable isotopes to examine watershed connectivity to ...

EPA Pesticide Factsheets

Water bodies within the USA are protected by the US Clean Water Act when they have a significant nexus to downstream navigable waters. As a research scientist with the US Environmental Protection Agency, I have used water stable isotopes to examine hydrologic connectivity dynamics. I will share two case studies. In the first case, we used the isotopic evaporation signal in water to examine wetland-stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie-pothole wetlands. Prairie-Pothole wetlands are a special case of wetlands whose protection needs to be determined under the Clean Water Rule. Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched prairie-pothole wetlands. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment. Using isotopic theory and discharge data, we estimated the area of surface water necessary to generate the evaporation signal found within Pipestem Creek over two years. Our results indicated that prairie-pothole wetlands were important sources of stream flow in Pipestem Creek throughout the summer, as well as during snowmelt. They also demonstrated that at the lowest flows, the stream itself became disconnected from headwater stream reaches. In the second ca

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

PubMed Central

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

2013-01-01

Chloromethane (CH3Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (ε) of −29‰ and −27‰ for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in 13C of untransformed CH3Cl was also observed, and similar isotope enrichment factors (ε) of −41‰ and −38‰ were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane. PMID:24019296

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

NASA Astrophysics Data System (ADS)

Rodovská, Zuzana; Magna, TomáÅ.¡; Žák, Karel; Kato, Chizu; Savage, Paul S.; Moynier, Frédéric; Skála, Roman; Ježek, Josef

2017-10-01

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn ( 10-20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ66Zn values between 1.7 and 3.7‰ (relative to JMC 3-0749 Lyon) and δ65Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ66Zn = -0.07 to +0.64‰; δ65Cu = -0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ65Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen-poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact-induced high-velocity jet of vapor and melts.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

Meteoritic Evidence for Multiple Early Enriched Reservoirs in the Martian Mantle

NASA Astrophysics Data System (ADS)

Armytage, R. M. G.; Debaille, V.; Brandon, A. D.; Agee, C. B.

2018-05-01

From isotopic systematics, the martian crustal reservoir represented by NWA 7034 cannot be the enriched end-member for the shergottites. This suggests multiple enriched reservoirs in the martian mantle formed by several differentiation events.

A new feature in the internal heavy isotope distribution in ozone

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

Bhattacharya, S. K., E-mail: skbhatta1@gmail.com; Liang, Mao-Chang; Savarino, Joel

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ({sup 18}O/{sup 16}O and {sup 17}O/{sup 16}O ratio) which does not follow normal mass fractionation rule: δ{sup 17}O ∼ 0.52{sup *}δ{sup 18}O, expressed as an anomaly Δ{sup 17}O = δ{sup 17}O − 0.52{sup *}δ{sup 18}O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ{sup 18}O (s) or δ{sup 18}O (as) (and similarly for δ{sup 17}O) as well asmore » position dependent isotope anomaly Δ{sup 17}O (s) and Δ{sup 17}O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ{sup 17}O (s) is zero. Consequently, Δ{sup 17}O (as) = 1.5 {sup *} Δ{sup 17}O (bulk) (named here simply as the “1.5 rule”) which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.« less

Salinity increases in the navajo aquifer in southeastern Utah

USGS Publications Warehouse

Naftz, D.L.; Spangler, L.E.

1994-01-01

Salinity increases in water in some parts of the Navajo aquifer in southeastern Utah have been documented previously. The purpose of this paper is to use bromide, iodide, and chloride concentrations and del oxygen-18 and deuterium values in water from the study area to determine if oil-field brines (OFB) could be the source of increased salinity. Mixing-model results indicate that the bromide-to-chloride X 10,000 weight ratio characteristic of OFB in and outside the study area could not be causing the bromide depletion with increasing salinity in the Navajo aquifer. Mixing-model results indicate that a mixture of one percent OFB with 99 percent Navajo aquifer water would more than double the bromide-to-chloride weight ratio, instead of the observed decrease in the weight ratio with increasing chloride concentration. The trend of the mixing line representing the isotopically enriched samples from the Navajo aquifer does not indicate OFB as the source of isotopically enriched water; however, the simulated isotopic composition of injection water could be a salinity source. The lighter isotopic composition of OFB samples from the Aneth, Ratherford, White Mesa Unit, and McElmo Creek injection sites relative to the Ismay site is a result of continued recycling of injection water mixed with various proportions of isotopically lighter make-up water from the alluvial aquifer along the San Juan River. A mixing model using the isotopic composition of the simulated injection water suggests that enriched samples from the Navajo aquifer are composed of 36 to 75 percent of the simulated injection water. However, chloride concentrations predicted by the isotopic mixing model are up to 13.4 times larger than the measured chloride concentrations in isotopically enriched samples from the Navajo aquifer, indicating that injection water is not the source of increased salinity. Geochemical data consistently show that OFB and associated injection water from the Greater Aneth Oil Field are not the source of salinity increases in the Navajo aquifer.

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

2010-01-01

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Investigating the effects of abyssal peridotite alteration on Si, Mg and Zn isotopes

NASA Astrophysics Data System (ADS)

Savage, P. S.; Wimpenny, J.; Harvey, J.; Yin, Q.; Moynier, F.

2013-12-01

Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si isotopes (similar to the serpentinites), however, some are isotopically heavy, relative to BSE. Such samples were found to have abundant chlorite, whose formation requires fluid with high Al activity, likely sourced from late-emplaced gabbroic dykes. The Zn of all 1268a samples are enriched in the lighter isotopes, implying the involvement of isotopically light sulfide precipitation during metasomatism [4]. The consistently heavy Mg isotope data suggest that seafloor alteration of peridotites can input an isotopically light Mg-bearing fluid to the ocean. Fluid composition is less easy to determine from the more complex behaviour observed in Si isotopes, although it is unlikely to substantially deviate from BSE, consistent with previous observations [8]. Finally, the strong enrichment in the lighter isotopes of Zn confirms that this isotope system could be used as a tracer of recycled serpentinised material at arc settings, as suggested in [4]. [1] Dick et al. (2003) Nature 426, 405-412; [2] Treguer and De La Rocha (2013) Ann. Rev. Mar. Sci. 5, 477-501; [3] Snow & Dick (1995) GCA, 59, 4219-4235; [4] Pons et al. (2011) PNAS 108(43) 17639-17643; [5] Bach et al., (2004) G3 5; [6] Tipper et al. (2006) EPSL 247, 267-279; [7] Opfergelt et al. (2012) Chem. Geol. 326, 113-122; [8] De La Rocha et al. (2000) GCA 64, 2467-2477.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Laser and gas centrifuge enrichment

NASA Astrophysics Data System (ADS)

Heinonen, Olli

2014-05-01

Principles of uranium isotope enrichment using various laser and gas centrifuge techniques are briefly discussed. Examples on production of high enriched uranium are given. Concerns regarding the possibility of using low end technologies to produce weapons grade uranium are explained. Based on current assessments commercial enrichment services are able to cover the global needs of enriched uranium in the foreseeable future.

Box-modeling of 15N/14N in mammals.

PubMed

Balter, Vincent; Simon, Laurent; Fouillet, Hélène; Lécuyer, Christophe

2006-03-01

The 15N/14N signature of animal proteins is now commonly used to understand their physiology and quantify the flows of nutrient in trophic webs. These studies assume that animals are predictably 15N-enriched relative to their food, but the isotopic mechanism which accounts for this enrichment remains unknown. We developed a box model of the nitrogen isotope cycle in mammals in order to predict the 15N/14N ratios of body reservoirs as a function of time, N intake and body mass. Results of modeling show that a combination of kinetic isotope fractionation during the N transfer between amines and equilibrium fractionation related to the reversible conversion of N-amine into ammonia is required to account for the well-established approximately 4 per thousand 15N-enrichment of body proteins relative to the diet. This isotopic enrichment observed in proteins is due to the partial recycling of 15N-enriched urea and the urinary excretion of a fraction of the strongly 15N-depleted ammonia reservoir. For a given body mass and diet delta15N, the isotopic compositions are mainly controlled by the N intake. Increase of the urea turnover combined with a decrease of the N intake lead to calculate a delta15N increase of the proteins, in agreement with the observed increase of collagen delta15N of herbivorous animals with aridity. We further show that the low delta15N collagen values of cave bears cannot be attributed to the dormancy periods as it is commonly thought, but inversely to the hyperphagia behavior. This model highlights the need for experimental investigations performed with large mammals in order to improve our understanding of natural variations of delta15N collagen.

Geochemical and isotopic investigation of the Laiwu-Zibo carbonatites from western Shandong Province, China, and implications for their petrogenesis and enriched mantle source

NASA Astrophysics Data System (ADS)

Ying, Jifeng; Zhou, Xinhua; Zhang, Hongfu

2004-08-01

Major and trace element and Nd-Sr isotope data of the Mesozoic Laiwu-Zibo carbonatites (LZCs) from western Shandong Province, China, provide clues to the petrogenesis and the nature of their mantle source. The Laiwu-Zibo carbonatites can be petrologically classified as calcio-, magnesio- and ferro-carbonatites. All these carbonatites show a similarity in geochemistry. On the one hand, they are extremely enriched in Ba, Sr and LREE and markedly low in K, Rb and Ti, which are similar to those global carbonatites, on the other hand, they have extremely high initial 87Sr/ 86Sr (0.7095-0.7106) and very low ɛNd (-18.2 to -14.3), a character completely different from those global carbonatites. The small variations in Sr and Nd isotopic ratios suggest that crustal contamination can not modify the primary isotopic compositions of LZC magmas and those values are representatives of their mantle source. The Nd-Sr isotopic compositions of LZCs and their similarity to those of Mesozoic Fangcheng basalts imply that they derived from an enriched lithospheric mantle. The formation of such enriched lithospheric mantle is connected with the major collision between the North China Craton (NCC) and the Yangtze Craton. Crustal materials from the Yangtze Craton were subducted beneath the NCC and melts derived from the subducted crust of the Yangtze Craton produced an enriched Mesozoic mantle, which is the source for the LZCs and Fangcheng basalts. The absence of alkaline silicate rocks, which are usually associated with carbonatites suggest that the LZCs originated from the mantle by directly partial melting.

Recycling Seamounts: Implications for Mantle Source Heterogeneities

NASA Astrophysics Data System (ADS)

Madrigal, P.; Gazel, E.

2016-12-01

Isolated seamounts formed away from plate boundaries and/or known hotspot tracks are widely distributed in the Earth's oceanic plates. Despite their pervasiveness, the origin and composition of the magmatic sources that create these seamounts are still unknown. Moreover, as the seamount provinces travel along with the oceanic plate towards subduction trenches these volcanic edifices become subducted materials that are later recycled into the mantle. Using radiogenic isotopes (Sr-Nd-Pb) from present-day non-plume ocean island basalts (OIB) sampled by drilling and dredging as well as by normal processes of accretion to subduction margins, we modeled the isotopic evolution of these enriched reservoirs to assess their role as discrete components contributing to upper mantle heterogeneity. Our evidence suggests that a highly enriched mantle reservoir can originate from OIB-type subducted material that gets incorporated and stirred throughout the upper mantle in a shorter time period ( 200 Ma-500 Ma) than other highly enriched components like ancient subducted oceanic crust (>1 Ga), thought to be the forming agent of the HIMU mantle reservoir endmember. Enriched signatures from intraplate volcanism can be described by mixing of a depleted component like DMM and an enriched reservoir like non-plume related seamounts. Our data suggests that the isotopic evolution in time of a seamount-province type of reservoir can acquire sufficiently enriched compositions to resemble some of the most enriched magmas on Earth. This "fast-forming" (between 200 and 500 Ma) enriched reservoir could also explain some of the enriched signatures commonly present in intraplate and EMORB magmas unrelated to deep mantle plume upwellings.

Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

USGS Publications Warehouse

Sturchio, N.C.; Keith, T.E.C.; Muehlenbachs, K.

1990-01-01

Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface (in situ temperatures ranging from 81 to 199??C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The ??18O values of the thirty-two analyzed silica samples (quartz, chalcedony, ??-cristobalite, and ??-cristobalite) range from -7.5 to +2.8???. About one third of the silica 7samples have ??18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7???) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have ??18O values higher (by 3.5 to 7.9???) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with deposition during transient boiling or rock-water exchange (fracturing) events. ?? 1990.

Barium isotopic compositions of oceanic basalts from São Miguel, Azores Archipelago

NASA Astrophysics Data System (ADS)

Yu, H.; Nan, X.; Huang, F.

2016-12-01

Oceanic island basalts (OIB) provide important information to decipher the processes of mantle convection and crustal material recycling1. OIBs from São Miguel, Azores Archipelago have extreme radiogenic isotope compositions2-3, representing an enriched component in their mantle source. However, the origins of the enriched mantle are still in debate. Previous studies proposed that the enriched component could be subducted terrigenous sediments2,4, delaminated subcontinental lithosphere5-6, recycled oceanic crust with evolved compositions (such as a subducted seamount)7, or enriched (E-MORB type) under-plated basalts which infiltrated the oceanic mantle lithosphere8. In this study, we use Ba isotopes to constrain the origin of enriched component beneath São Miguel because Ba isotopes can be significantly fractionated at the Earth's surface with low temperature environment than in the mantle with high temperature9-10. We analyzed Ba isotopes of 15 basalts from São Miguel. Although these samples have large variations of 87Sr/86Sr (0.703440-0.705996), 206Pb/204Pb (19.319-20.095) and 187Os/188Os (0.127-0.161), they have limited variation of 137Ba/134Ba (-0.003 to +0.048‰). The average 137Ba/134Ba of São Miguel basalts is 0.019±0.033‰ (n=15, 2SD), which is in the range of mantle (0.026±0.090‰, n=32, 2SD)9, indicating there is no surface material in the mantle source of São Miguel. The enriched source of São Miguel could be evolved material from the mantle. 1. Hofmann, 1997, Nature; 2. Hawkesworth et al., 1979, Nature; 3. White et al., 1979, CMP; 4. Turner et al., 1997, CG; 5. Widom et al., 1997, CG; 6. Moreira et al., 1999, EPSL; 7. Beier et al., 2007, EPSL; 8. Elliott et al., 2007, GCA; 9. Huang et al., 2015, Goldschmidt abs 1331; 10. Nan et al., 2016, Goldschmidt abs 2246.

16O enrichments in aluminum-rich chondrules from ordinary chondrites

NASA Astrophysics Data System (ADS)

Russell, Sara S.; MacPherson, Glenn J.; Leshin, Laurie A.; McKeegan, Kevin D.

2000-12-01

The oxygen isotopic compositions of seven Al-rich chondrules from four unequilibrated ordinary chondrites were measured in situ using an ion microprobe. On an oxygen three isotope plot, the data are continuous with the ordinary chondrite ferromagnesian chondrule field but extend it to more 16O-enriched values along a mixing line of slope=0.83±0.09, with the lightest value recorded at δ18O=-15.7±1.8‰ and δ17O=-13.5±2.6‰. If Al-rich chondrules were mixtures of ferromagnesian chondrules and CAI material, their bulk chemical compositions would require them to exhibit larger 16O enrichments than we observe. Therefore, Al-rich chondrules are not simple mixtures of these two components. Three chondrules exhibit significant internal isotopic heterogeneity indicative of partial exchange with a gaseous reservoir. Porphyritic Al-rich chondrules are consistently 16O-rich relative to nonporphyritic ones, suggesting that degree of melting is a key factor and pointing to a nebular setting for the isotopic exchange process. Because Al-rich chondrules are closely related to ferromagnesian chondrules, their radiogenic Mg isotopic abundances can plausibly be applied to help constrain the timing or location of chondrule formation.

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

NASA Technical Reports Server (NTRS)

Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

1997-01-01

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1987-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1977-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine).

PubMed

Vystavna, Yuliya; Diadin, Dmytro; Huneau, Frédéric

2018-05-01

Stable isotopes of hydrogen ( 2 H) and oxygen ( 18 O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November-March and an enrichment in April-October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.

Noble gases in the Murchison meteorite - Possible relics of s-process nucleosynthesis

NASA Technical Reports Server (NTRS)

Srinivasan, B.; Anders, E.

1978-01-01

The Murchison carbonaceous chondrite contains a new type of xenon component, enriched by up to 50 percent in five of the nine stable xenon isotopes, mass numbers 128 to 132. This component is released at 1200 to 1600 C from a severely etched mineral fraction. Krypton shows a similar but smaller enrichment in the isotopes 80 and 82. Neon and helium released in the same interval also are quite anomalous, being highly enriched in the isotopes 22 and 3. These patterns are strongly suggestive of three nuclear processes believed to take place in red giants: the s process (neutron capture on a slow time scale), helium burning, and hydrogen shell burning. If this interpretation is correct, then primitive meteorites contain yet another kind of alien, presolar material: dust grains ejected from red giants.

Minor isotope safeguards techniques (MIST): Analysis and visualization of gas centrifuge enrichment plant process data using the MSTAR model

NASA Astrophysics Data System (ADS)

Shephard, Adam M.; Thomas, Benjamin R.; Coble, Jamie B.; Wood, Houston G.

2018-05-01

This paper presents a development related to the use of minor isotope safeguards techniques (MIST) and the MSTAR cascade model as it relates to the application of international nuclear safeguards at gas centrifuge enrichment plants (GCEPs). The product of this paper is a derivation of the universal and dimensionless MSTAR cascade model. The new model can be used to calculate the minor uranium isotope concentrations in GCEP product and tails streams or to analyze, visualize, and interpret GCEP process data as part of MIST. Applications of the new model include the detection of undeclared feed and withdrawal streams at GCEPs when used in conjunction with UF6 sampling and/or other isotopic measurement techniques.

Daily Variation of Isotope Ratios in Mars Atmospheric Carbon Dioxide

NASA Astrophysics Data System (ADS)

Livengood, Timothy A.; Kostiuk, Theodor; Kolasinski, John R.; Hewagama, Tilak; Henning, Wade G.; Sornig, Manuela; Stangier, Tobias; Krause, Pia; Sonnabend, Guido; Mahaffy, Paul R.

2014-11-01

The atmosphere of Mars has been shown by ground based high-resolution infrared spectroscopy and in situ measurements with the Phoenix lander and Mars Science Laboratory Curiosity rover to be enriched in C and O heavy isotopes, consistent with preferential loss of light isotopes in eroding Mars’ primordial atmosphere. The relative abundance of heavy isotopes, combined with contemporary measurements of loss rates to be obtained with MAVEN, will enable estimating the primordial atmospheric inventory on Mars. IR spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF has resolved transitions of all three singly-substituted minor isotopologues of carbon dioxide in addition to the normal isotope, enabling remote measurements of all the carbon and oxygen isotope ratios as a function of latitude, longitude, and time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with contemporary in situ measurements by the Curiosity rover to investigate the degree of agreement between in situ and remote methods and potentially to calibrate the spectroscopic constants required to accurately evaluate isotope ratios all over Mars.

Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

NASA Astrophysics Data System (ADS)

Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.

2006-12-01

Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in stalagmites as the supply rate of dripping water changes. Also, different texture in stalagmites can be used as another criteria to determine the degree of equilibrium.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Goldhaber, M.B.

1987-01-01

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate ??34S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the ??34S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be -5.2%. and the detrital sulfur input was estimated to be -6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients. ?? 1987.

Early diagenesis and organic matter preservation--A molecular stable isotope perspective

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

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

1992-01-01

Through new developments in stable isotope capability, gas chromatography coupled to a stable isotope ratio mass spectrometer (GC/IRMS), the molecular pathways of the diagenetic reactions can be observed on the components themselves. The authors report the results of laboratory-controlled degradation experiments of fresh organic substrates. Isotopically resolvable materials were used. Seagrass showed slight enrichments in [delta]N-15 with little change in [delta]C-13 following four weeks of decomposition. During that period the identifiable amino acid content decreased by approx. 50% for each amino acid. Mixtures of marine sediment with the same seagrass showed enrichments in nitrogen with associated depletions in carbon isotopicmore » compositions over the same time span. Control experiments on the sediments without added fresh seagrass showed no change in isotopic content. These changes are attributed to hydrolysis, deamination and decarboxylation reactions. Isotopic fractionations of similar size and direction have been observed in laboratory studies on peptide hydrolysis and natural samples of particulate organic materials. At the molecular level, using GC/IRMS, certain amino acids are seen to decrease in C-13 content while others become increasingly enriched in C-13. Similar reactions are seen in carbohydrates. The molecular isotope approach indicates that the process of diagenesis and preservation is significantly more complex than simple breakdown and loss. A large portion of the organic matter eventually preserved in organic-rich deposits can be attributed to new production in the deposit.« less

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means. 3 figures.

Heat deposition analysis for the High Flux Isotope Reactor’s HEU and LEU core models

DOE PAGES

Davidson, Eva E.; Betzler, Benjamin R.; Chandler, David; ...

2017-08-01

The High Flux Isotope Reactor at Oak Ridge National Laboratory is an 85 MW th pressurized light-water-cooled and -moderated flux-trap type research reactor. The reactor is used to conduct numerous experiments, advancing various scientific and engineering disciplines. As part of an ongoing program sponsored by the US Department of Energy National Nuclear Security Administration Office of Material Management and Minimization, studies are being performed to assess the feasibility of converting the reactor’s highly enriched uranium fuel to low-enriched uranium fuel. To support this conversion project, reference models with representative experiment target loading and explicit fuel plate representation were developed andmore » benchmarked for both fuels to (1) allow for consistent comparison between designs for both fuel types and (2) assess the potential impact of low-enriched uranium conversion. These high-fidelity models were used to conduct heat deposition analyses at the beginning and end of the reactor cycle and are presented herein. This article (1) discusses the High Flux Isotope Reactor models developed to facilitate detailed heat deposition analyses of the reactor’s highly enriched and low-enriched uranium cores, (2) examines the computational approach for performing heat deposition analysis, which includes a discussion on the methodology for calculating the amount of energy released per fission, heating rates, power and volumetric heating rates, and (3) provides results calculated throughout various regions of the highly enriched and low-enriched uranium core at the beginning and end of the reactor cycle. These are the first detailed high-fidelity heat deposition analyses for the High Flux Isotope Reactor’s highly enriched and low-enriched core models with explicit fuel plate representation. Lastly, these analyses are used to compare heat distributions obtained for both fuel designs at the beginning and end of the reactor cycle, and they are essential for enabling comprehensive thermal hydraulics and safety analyses that require detailed estimates of the heat source within all of the reactor’s fuel element regions.« less

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

PubMed

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

2008-09-01

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

Process for preparing a chemical compound enriched in isotope content

DOEpatents

Michaels, Edward D.

1982-01-01

A process to prepare a chemical enriched in isotope content which includes: (a) A chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; (b) the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; (c) the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; (d) the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products.

Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

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

Knight, K; Kita, N; Mendybaev, R

2009-06-18

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquidsmore » (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.« less

Preparation and characterisation of isotopically enriched Ta2O5 targets for nuclear astrophysics studies

NASA Astrophysics Data System (ADS)

Caciolli, A.; Scott, D. A.; Di Leva, A.; Formicola, A.; Aliotta, M.; Anders, M.; Bellini, A.; Bemmerer, D.; Broggini, C.; Campeggio, M.; Corvisiero, P.; Depalo, R.; Elekes, Z.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Imbriani, G.; Junker, M.; Marta, M.; Menegazzo, R.; Napolitani, E.; Prati, P.; Rigato, V.; Roca, V.; Rolfs, C.; Rossi Alvarez, C.; Somorjai, E.; Salvo, C.; Straniero, O.; Strieder, F.; Szücs, T.; Terrasi, F.; Trautvetter, H. P.; Trezzi, D.

2012-10-01

The direct measurement of reaction cross-sections at astrophysical energies often requires the use of solid targets of known thickness, isotopic composition, and stoichiometry that are able to withstand high beam currents for extended periods of time. Here, we report on the production and characterisation of isotopically enriched Ta2O5 targets for the study of proton-induced reactions at the Laboratory for Underground Nuclear Astrophysics facility of the Laboratori Nazionali del Gran Sasso. The targets were prepared by anodisation of tantalum backings in enriched water (up to 66% in 17O and up to 96% in 18O. Special care was devoted to minimising the presence of any contaminants that could induce unwanted background reactions with the beam in the energy region of astrophysical interest. Results from target characterisation measurements are reported, and the conclusions for proton capture measurements with these targets are drawn.

Noble Gases in the Murchison Meteorite: Possible Relics of s-Process Nucleosynthesis.

PubMed

Srinivasan, B; Anders, E

1978-07-07

The Murchison carbonaceous chondrite contains a new type of xenon component, enriched by up to 50 percent in five of the nine stable xenon isotopes, mass numbers 128 to 132. This component, comprising 5 x 10(-5) of the total xenon in the meteorite, is released at 1200 degrees to 1600 degrees C from a severely etched mineral fraction, and probably resides in some refractory mineral. Krypton shows a similar but smaller enrichment in the isotopes 80 and 82. Neon and helium released in the same interval also are quite anomalous, being highly enriched in the isotopes 22 and 3. These patterns are strongly suggestive of three nuclear processes believed to take place in red giants: the s process (neutron capture on a slow time scale), helium burning, and hydrogen shell burning. If this interpretation is correct, then primitive meteorites contain yet another kind of alien, presolar material: dust grains ejected from red giants.

Simulating Isotope Enrichment by Gaseous Diffusion

NASA Astrophysics Data System (ADS)

Reed, Cameron

2015-04-01

A desktop-computer simulation of isotope enrichment by gaseous diffusion has been developed. The simulation incorporates two non-interacting point-mass species whose members pass through a cascade of cells containing porous membranes and retain constant speeds as they reflect off the walls of the cells and the spaces between holes in the membranes. A particular feature is periodic forward recycling of enriched material to cells further along the cascade along with simultaneous return of depleted material to preceding cells. The number of particles, the mass ratio, the initial fractional abundance of the lighter species, and the time between recycling operations can be chosen by the user. The simulation is simple enough to be understood on the basis of two-dimensional kinematics, and demonstrates that the fractional abundance of the lighter-isotope species increases along the cascade. The logic of the simulation will be described and results of some typical runs will be presented and discussed.

New method for GC/FID and GC-C-IRMS Analysis of plasma free fatty acid concentration and isotopic enrichment

PubMed Central

Kangani, Cyrous O.; Kelley, David E.; DeLany, James P.

2008-01-01

A simple, direct and accurate method for the determination of concentration and enrichment of free fatty acids in human plasma was developed. The validation and comparison to a conventional method are reported. Three amide derivatives, dimethyl, diethyl and pyrrolidide, were investigated in order to achieve optimal resolution of the individual fatty acids. This method involves the use of dimethylamine/Deoxo-Fluor to derivatize plasma free fatty acids to their dimethylamides. This derivatization method is very mild and efficient, and is selective only towards free fatty acids so that no separation from a total lipid extract is required. The direct method gave lower concentrations for palmitic acid and stearic acid and increased concentrations for oleic acid and linoleic acid in plasma as compared to methylester derivative after thin-layer chromatography. The [13C]palmitate isotope enrichment measured using direct method was significantly higher than that observed with the BF3/MeOH-TLC method. The present method provided accurate and precise measures of concentration as well as enrichment when analyzed with gas chromatography combustion-isotope ratio-mass spectrometry. PMID:18757250

New method for GC/FID and GC-C-IRMS analysis of plasma free fatty acid concentration and isotopic enrichment.

PubMed

Kangani, Cyrous O; Kelley, David E; Delany, James P

2008-09-15

A simple, direct and accurate method for the determination of concentration and enrichment of free fatty acids (FFAs) in human plasma was developed. The validation and comparison to a conventional method are reported. Three amide derivatives, dimethyl, diethyl and pyrrolidide, were investigated in order to achieve optimal resolution of the individual fatty acids. This method involves the use of dimethylamine/Deoxo-Fluor to derivatize plasma free fatty acids to their dimethylamides. This derivatization method is very mild and efficient, and is selective only towards FFAs so that no separation from a total lipid extract is required. The direct method gave lower concentrations for palmitic acid and stearic acid and increased concentrations for oleic acid and linoleic acid in plasma as compared to methyl ester derivative after thin-layer chromatography. The [(13)C]palmitate isotope enrichment measured using direct method was significantly higher than that observed with the BF(3)/MeOH-TLC method. The present method provided accurate and precise measures of concentration as well as enrichment when analyzed with gas chromatography combustion-isotope ratio-mass spectrometry.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C.P.; Rockwood, S.D.; Jensen, R.J.; Lyman, J.L.; Aldridge, J.P. III.

1987-04-07

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO[sub 2] laser light may be used to highly enrich [sup 34]S in natural SF[sub 6] and [sup 11]B in natural BCl[sub 3]. 8 figs.

Transport, biodegradation and isotopic fractionation of chlorinated ethenes: modeling and parameter estimation methods

NASA Astrophysics Data System (ADS)

Béranger, Sandra C.; Sleep, Brent E.; Lollar, Barbara Sherwood; Monteagudo, Fernando Perez

2005-01-01

An analytical, one-dimensional, multi-species, reactive transport model for simulating the concentrations and isotopic signatures of tetrachloroethylene (PCE) and its daughter products was developed. The simulation model was coupled to a genetic algorithm (GA) combined with a gradient-based (GB) method to estimate the first order decay coefficients and enrichment factors. In testing with synthetic data, the hybrid GA-GB method reduced the computational requirements for parameter estimation by a factor as great as 300. The isotopic signature profiles were observed to be more sensitive than the concentration profiles to estimates of both the first order decay constants and enrichment factors. Including isotopic data for parameter estimation significantly increased the GA convergence rate and slightly improved the accuracy of estimation of first order decay constants.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, C.A.; Worden, E.F.

1995-08-22

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

NASA Astrophysics Data System (ADS)

Borysiuk, Maciek; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

2015-04-01

The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: 16O, 17O and 18O. We procured samples highly enriched with all three isotopes. Isotopes 16O and 18O were easily detected in the enriched samples, but no significant signal from 17O was detected in the same samples. The measured yield was too low to detect 18O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with 16O was clearly visible.

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

PubMed

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

2010-06-01

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

The role of symmetry in the mass independent isotope effect in ozone

PubMed Central

Michalski, Greg; Bhattacharya, S. K.

2009-01-01

Understanding the internal distribution of “anomalous” isotope enrichments has important implications for validating theoretical postulates on the origin of these enrichments in molecules such as ozone and for understanding the transfer of these enrichments to other compounds in the atmosphere via mass transfer. Here, we present an approach, using the reaction NO2− + O3, for assessing the internal distribution of the Δ17O anomaly and the δ18O enrichment in ozone produced by electric discharge. The Δ17O results strongly support the symmetry mechanism for generating mass independent fractionations, and the δ18O results are consistent with published data. Positional Δ17O and δ18O enrichments in ozone can now be more effectively used in photochemical models that use mass balance oxygen atom transfer mechanisms to infer atmospheric oxidation chemistry. PMID:19307571

Positive parity states and some electromagnetic transition properties of even-odd europium isotopes

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

Yazar, Harun Resit, E-mail: yazar@nevsehir.edu.tr

2013-06-15

The positive-parity low-spin states of even-odd Europium isotopes ({sup 151-155}Eu) were studied within the framework of the interacting boson-fermion model. The calculated positive low-spin state energy spectra of the odd Eu isotope were found to agree quite well with the experimental data. The B(E2) values were also calculated and it was found that the calculated positive-parity low-spin state energy spectra of the odd-A Eu isotopes agree quite well with the experimental data.

Titanium Isotopes Link the High 3He/4He Reservoir to Continent Formation

NASA Astrophysics Data System (ADS)

Millet, M. A.; Jackson, M. G.; Dauphas, N.; Burton, K. W.; Williams, H. M.; Kurz, M. D.; Doucelance, R.; Smithies, H.; Champion, D. C.; Nowell, G. M.

2016-12-01

Elevated 3He/4He ratios found in ocean island basalts (OIB) argue for the survival of an early-formed reservoir (>4.5 Ga) in the Earth's mantle [1]. However, its nature remains debated. A characteristic of high 3He/4He OIBs is their anomalous enrichment in Ti abundance relative to elements of similar incompatibility (Sm and Tb). Here we use a new geochemical tool, the stable isotopes of Titanium, to investigate the origin of Ti enrichment of high 3He/4He OIBs. Recent work [2] has shown that Ti isotopes are a powerful tracer of oxide-melt equilibrium in magmatic systems. Results show that primitive OIB samples from localities associated with low 3He/4He ratios (≤15 R/Ra) have δ49Ti values within error of the mantle (δ49Ti=0.005±0.005 [2]) and chondrite values (+0.004±0.010 [3]) regardless of their Ti anomaly (0.93He/4He ratios (>25R/Ra) display δ49Ti values ranging from mantle-like to enriched in light isotopes (up to -0.065‰±0.005) that are negatively correlated with their Ti/Ti* and uncorrelated to indices of magma differentiation. This indicates that i) elevated Ti/Ti* in high 3He/4He OIBs is a mantle source signature and ii) that the high 3He/4He reservoir is enriched in light isotopes of Ti relative to the BSE. This enrichment in light isotopes is balanced by the heavy δ49Ti values and negative Ti/Ti* of Archean Tonalite-Throndhjemite-Granodiorite samples (TTG) from the Pilbara and Yilgarn Craton (+0.20<δ49Ti<+0.40), a proxy for early-formed, juvenile continental crust. Given the chondritic composition of the Earth's mantle and the inability of the typical mantle lithologies to fractionate Ti isotopes, this implies that the Ti enrichment of the high 3He/4He mantle reservoir is linked to the recycling of residues of partial melting events in the presence of rutile (TiO2), a process that drove continent formation in the Archean and possibly earlier. In addition, since these residues cannot display elevated 3He/4He ratios, it requires the Ti-He signature of the high 3He/4He reservoir is due to recycling of entire slab packages. [1] Rizo et al., Science, 2016 [2] Millet et al., EPSL, 2016 [3] Greber et al., LPSC, 2016

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40Ca. On the other hand, 40Ca may desorb more easily, especially if the bond strength is lower as in the case of aragonite. For kinetic oxygen isotopic fractionation, the faster deprotonation of HC16O3- and the faster incorporation of C16O32- at the surfaces causes a smaller enrichment of 18O in all three polymorphs, which will be preserved at higher precipitation rates. In consequence to the different behavior of calcium and oxygen isotopes, they can be useful for multiproxy applications. Thereby calcium isotopes can be used to identify kinetic effects, especially if both aragonite and calcite, can be analyzed in one sample. Oxygen isotopes are more strongly related to temperature. [1]A. Niedermayr, S.J. Köhler and M. Dietzel (2013), Chemical Geology, 340, 105-120.

Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes

NASA Technical Reports Server (NTRS)

Drummond, C. N.; Patterson, W. P.; Walker, J. C.

1995-01-01

Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.

Axi-symmetrical flow reactor for .sup.196 Hg photochemical enrichment

DOEpatents

Grossman, Mark W.

1991-01-01

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, .sup.196 Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired .sup.196 Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith.

Fractionation of carbon (13C/12C) isotopes in glycine decarboxylase reaction.

PubMed

Ivlev, A A; Bykova, N V; Igamberdiev, A U

1996-05-20

Fractionation of carbon isotopes (13C/12C) by glycine decarboxylase (GDC) was investigated in mitochondrial preparations isolated from photosynthetic tissues of different plants (Pisum, Medicago, Triticum, Hordeum, Spinacia, Brassica, Wolffia). 20 mM glycine was supplied to mitochondria, and the CO2 formed was absorbed and analyzed for isotopic content. CO2 evolved by mitochondria of Pisum was enriched up to 8% in 12C compared to the carboxylic atom of glycine. CO2 evolved by mitochondria of the other plants investigated was enriched by 5-16% in 13C. Carbon isotope effects were sensitive to reaction conditions (pH and the presence of GDC cofactors). Theoretical treatment of the reaction mechanism enabled us to conclude that the value and even the sign of the carbon isotope effect in glycine decarboxylation depend on the contribution of the enzyme-substrate binding step and of the decarboxylation step itself to the overall reaction rate. Therefore, the fractionation of carbon isotopes in GDC reaction was revealed which provides essential isotopic effects in plants in addition to the well-known effect of carbon isotope fractionation by the central photosynthetic enzyme, ribulose-1,5-biphosphate carboxylase.

Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

PubMed Central

Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

2014-01-01

The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuous-flow technique using capillary GC/combustion IRMS. Quadriceps muscles were removed from four Sprague–Dawley rats after each was infused at a different rate with (1-13C)leucine for 6–8 h. Muscle leucine enrichment (at.% excess) measured by both methods differed by less than 4%, except at low (13C)leucine enrichments (<0.03 at.% excess). In addition, capillary GC/combustion IRMS was used to assess muscle (13C)leucine enrichment and fractional muscle protein synthesis rate in ten normal young men and women infused with (1,2-13C2)leucine for 12–14 h. This approach reduced the variability of the isotope abundance measure and gave estimates of muscle protein synthesis rate (0.050 ± 0.011% h−1 (mean ± SEM); range = 0.023–0.147% h−1) that agree with published values determined using the standard analytical approach. The measurement of (13C)leucine enrichment from skeletal muscle protein by capillary GC/combustion IRMS provides a simple, acceptable and practical alternative to preparative GC/ninhydrin IRMS. PMID:1420371

Use of Nitrogen-15-Enriched Escherichia coli as a Bacterial Tracer in Karst Aquifers.

PubMed

Ward, James W; Warden, John G; Bandy, Ashley M; Fryar, Alan E; Brion, Gail M; Macko, Stephen A; Romanek, Christopher S; Coyne, Mark S

2016-11-01

Karst aquifers are susceptible to contamination by microorganisms, but relatively few studies have used bacteria as tracers. We demonstrate the utility of Escherichia coli enriched in the stable isotope nitrogen-15 ( 15 N) as a novel bacterial tracer. Nonpathogenic E. coli from two springs in central Kentucky were grown on 15 N-enriched media. Survival of E. coli and persistence of the isotopic signal were assessed in two sets of laboratory experiments conducted with sterilized spring water in dark microcosms at 14 °C. First, isotopically labeled bacteria survived for 130 d at concentrations within one log unit of the average initial value, and there was no significant difference in δ 15 N values from Day 1 to Day 130. Second, water samples with E. coli were inoculated with either of two different species of protozoa (Tetrahymena pyriformis or Colpoda steinii). During 7 d, δ 15 N values increased in T. pyriformis while bacterial populations decreased. In a field test, following a 2.1-cm rainfall, 15 N-labeled E. coli, solutes (rhodamine WT dye and bromide), and latex microspheres were injected into a sinkhole approximately 530 m upgradient of a spring. Breakthrough of all tracers coincided, but microspheres were remobilized by subsequent storms, unlike other tracers. Enriched E. coli exhibited more tailing than solute tracers during the initial storm-flow recession. These results indicate that 15 N-enriched E. coli is a viable tracer of bacterial transport in karst aquifers, although predation may attenuate the isotopic signal in systems that are not rapidly flushed. © 2016, National Ground Water Association.

USING MUSSEL ISOTOPE RATIOS TO ASSESS ANTHROPOGEN NITROGEN INPUTS TO COASTAL ECOSYSTEMS

EPA Science Inventory

The stable nitrogen isotope ratio in ribbed mussel (Geukensia demissus) tissue was investigated as an indicator of the source of nitrogen inputs to coastal salt marshes. Mussels fed a diet of 15N enriched algae in the laboratory showed an increase in tissue nitrogen isotope rati...

Ultrahigh thermal conductivity of isotopically enriched silicon

NASA Astrophysics Data System (ADS)

Inyushkin, Alexander V.; Taldenkov, Alexander N.; Ager, Joel W.; Haller, Eugene E.; Riemann, Helge; Abrosimov, Nikolay V.; Pohl, Hans-Joachim; Becker, Peter

2018-03-01

Most of the stable elements have two and more stable isotopes. The physical properties of materials composed of such elements depend on the isotopic abundance to some extent. A remarkably strong isotope effect is observed in the phonon thermal conductivity, the principal mechanism of heat conduction in nonmetallic crystals. An isotopic disorder due to random distribution of the isotopes in the crystal lattice sites results in a rather strong phonon scattering and, consequently, in a reduction of thermal conductivity. In this paper, we present new results of accurate and precise measurements of thermal conductivity κ(T) for silicon single crystals having three different isotopic compositions at temperatures T from 2.4 to 420 K. The highly enriched crystal containing 99.995% of 28Si, which is one of the most perfect crystals ever synthesized, demonstrates a thermal conductivity of about 450 ± 10 W cm-1 K-1 at 24 K, the highest measured value among bulk dielectrics, which is ten times greater than the one for its counterpart natSi with the natural isotopic constitution. For highly enriched crystal 28Si and crystal natSi, the measurements were performed for two orientations [001] and [011], a magnitude of the phonon focusing effect on thermal conductivity was determined accurately at low temperatures. The anisotropy of thermal conductivity disappears above 31 K. The influence of the boundary scattering on thermal conductivity persists sizable up to much higher temperatures (˜80 K). The κ(T) measured in this work gives the most accurate approximation of the intrinsic thermal conductivity of single crystal silicon which is determined solely by the anharmonic phonon processes and diffusive boundary scattering over a wide temperature range.

Li Isotopes as Tracers of Fluid-Rock Interactions in Oceanic Hydrothermal Systems: Evidence From the Hess Deep Rift

NASA Astrophysics Data System (ADS)

Brant, C. O.; Coogan, L. A.; Gillis, K. M.

2004-12-01

Li isotopes have the potential to be powerful tracers of fluid-rock interactions at mid-ocean ridge hydrothermal systems due to the large isotopic difference between seawater (δ7Li = 31‰) and fresh MORB (δ7Li = 1.5 to 5.6 ‰). Sampling programs along tectonic escarpments at Hess Deep provide an ideal suite to examine the spatial variability of Li mobility and Li isotopic content within young (1 Ma) lavas and sheeted dikes formed at the fast-spreading East Pacific Rise towards the end of a segment. Previous work has shown that the lavas are relatively fresh, with minor alteration to clay minerals and Fe oxyhydroxides. Sheeted dikes are variably altered to amphibole-dominated assemblages, with localized zones where chlorite dominates. Sr and O isotope data correlate with these regional patterns. Preliminary data, collected by Thermo X-series quadrupole ICP-MS, show that the lavas have similar Li concentrations to fresh MORB (5 to 6 ppm) and are slightly enriched in δ7Li (4.1 to 7.7 ‰). There is a positive correlation between Li content and δ7Li within the lavas, however, the trend is not a simple mixing line between seawater and fresh MORB, being offset to lower δ7Li in the altered component. Similar to previous studies, these relationships support the prediction that 6Li is preferentially retained in low temperature clay minerals. Sheeted dykes are depleted in Li (0.8-4.63 ppm) and most samples are enriched in δ7Li (6.7-15.4 ‰) relative to fresh MORB. These samples show an inverse relationship between decreasing concentration and increasing isotopic enrichment. This implies that 6Li is not simply preferentially retained in the replacement mineral assemblages. The degree of isotopic enrichment appears to increase with increasing clinopyroxene alteration, and is greatest for amphibolite dominated assemblages. A broad positive correlation between Li concentration and δ18O is observed in the dikes. Thus Li isotopes are sensitive indicators of the nature and extent of hydrothermal interactions for both high and low temperature processes.

Li Isotopes as Tracers of Fluid-Rock Interactions in Oceanic Hydrothermal Systems: Evidence From the Hess Deep Rift

NASA Astrophysics Data System (ADS)

Brant, C. O.; Coogan, L. A.; Gillis, K. M.

2007-12-01

Li isotopes have the potential to be powerful tracers of fluid-rock interactions at mid-ocean ridge hydrothermal systems due to the large isotopic difference between seawater (δ7Li = 31‰) and fresh MORB (δ7Li = 1.5 to 5.6 ‰). Sampling programs along tectonic escarpments at Hess Deep provide an ideal suite to examine the spatial variability of Li mobility and Li isotopic content within young (1 Ma) lavas and sheeted dikes formed at the fast-spreading East Pacific Rise towards the end of a segment. Previous work has shown that the lavas are relatively fresh, with minor alteration to clay minerals and Fe oxyhydroxides. Sheeted dikes are variably altered to amphibole-dominated assemblages, with localized zones where chlorite dominates. Sr and O isotope data correlate with these regional patterns. Preliminary data, collected by Thermo X-series quadrupole ICP-MS, show that the lavas have similar Li concentrations to fresh MORB (5 to 6 ppm) and are slightly enriched in δ7Li (4.1 to 7.7 ‰). There is a positive correlation between Li content and δ7Li within the lavas, however, the trend is not a simple mixing line between seawater and fresh MORB, being offset to lower δ7Li in the altered component. Similar to previous studies, these relationships support the prediction that 6Li is preferentially retained in low temperature clay minerals. Sheeted dykes are depleted in Li (0.8-4.63 ppm) and most samples are enriched in δ7Li (6.7-15.4 ‰) relative to fresh MORB. These samples show an inverse relationship between decreasing concentration and increasing isotopic enrichment. This implies that 6Li is not simply preferentially retained in the replacement mineral assemblages. The degree of isotopic enrichment appears to increase with increasing clinopyroxene alteration, and is greatest for amphibolite dominated assemblages. A broad positive correlation between Li concentration and δ18O is observed in the dikes. Thus Li isotopes are sensitive indicators of the nature and extent of hydrothermal interactions for both high and low temperature processes.

Enrichments of the mantle sources beneath the Southern Volcanic Zone (Andes) by fluids and melts derived from abraded upper continental crust

NASA Astrophysics Data System (ADS)

Holm, Paul Martin; Søager, Nina; Dyhr, Charlotte Thorup; Nielsen, Mia Rohde

2014-05-01

Mafic basaltic-andesitic volcanic rocks from the Andean Southern Volcanic Zone (SVZ) exhibit a northward increase in crustal components in primitive arc magmas from the Central through the Transitional and Northern SVZ segments. New elemental and Sr-Nd-high-precision Pb isotope data from the Quaternary arc volcanic centres of Maipo (NSVZ) and Infernillo and Laguna del Maule (TSVZ) are argued to reflect mainly their mantle source and its melting. For the C-T-NSVZ, we identify two types of source enrichment: one, represented by Antuco in CSVZ, but also present northward along the arc, was dominated by fluids which enriched a pre-metasomatic South Atlantic depleted MORB mantle type asthenosphere. The second enrichment was by melts having the characteristics of upper continental crust (UCC), distinctly different from Chile trench sediments. We suggest that granitic rocks entered the source mantle by means of subduction erosion in response to the northward increasingly strong coupling of the converging plates. Both types of enrichment had the same Pb isotope composition in the TSVZ with no significant component derived from the subducting oceanic crust. Pb-Sr-Nd isotopes indicate a major crustal compositional change at the southern end of the NSVZ. Modelling suggests addition of around 2 % UCC for Infernillo and 5 % for Maipo.

Loss of oxygen, silicon, sulfur, and potassium from the lunar regolith

NASA Technical Reports Server (NTRS)

Clayton, R. N.; Mayeda, T. K.; Hurd, J. M.

1974-01-01

The processes of formation and maturation of lunar soils lead to enrichments in the heavy stable isotopes of oxygen, silicon, sulfur, and potassium. The isotopic enrichment implies substantial losses of these elements from the moon. Vaporization by micrometeorite impact and by ion sputtering have removed at least 1% of the mass of the regolith. The losses of sulfur and potassium amount to at least 20-30% of their original abundance in the regolith.

Utilization of non-weapons-grade plutonium and highly enriched uranium with breeding of the 233U isotope in the VVER reactors using thorium and heavy water

NASA Astrophysics Data System (ADS)

Marshalkin, V. E.; Povyshev, V. M.

2015-12-01

A method for joint utilization of non-weapons-grade plutonium and highly enriched uranium in the thorium-uranium—plutonium oxide fuel of a water-moderated reactor with a varying water composition (D2O, H2O) is proposed. The method is characterized by efficient breeding of the 233U isotope and safe reactor operation and is comparatively simple to implement.

Lead Isotope Compositions of Acid Residues from Olivine-Phyric Shergottite Tissint: Implications for Heterogeneous Shergottite Source Reservoirs

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

2015-01-01

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions and trace element abundances. These correlations have been interpreted as indicating the presence of a reduced, incompatible element- depleted reservoir and an oxidized, incompatible- element-enriched reservoir. The former is clearly a depleted mantle source, but there is ongoing debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former requires the ancient Martian crust to be the enriched source (crustal assimilation), whereas the latter requires isolation of a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and trace element concentration analyses of sequential acid-leaching fractions (leachates and the final residues) from the geochemically depleted olivine-phyric shergottite Tissint. The results suggest that the Tissint magma is not isotopically uniform and sampled at least two geochemical source reservoirs, implying that either crustal assimilation or magma mixing would have played a role in the Tissint petrogenesis.

Discrimination of carbon and nitrogen isotopes from milk to serum and vibrissae in Alaska Steller sea lions (Eumetopias jubatus)

USGS Publications Warehouse

Stegall, V.K.; Farley, Sean D.; Rea, Lorrie D.; Pitcher, K.W.; Rye, R.O.; Kester, C.L.; Stricker, C.A.; Bern, C.R.

2008-01-01

Knowledge of diet-tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared ??13C and ??15N of paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion (Eumetopias jubatus (Schreber, 1776)) pups (1-11 months) and juveniles (14-27 months) to estimate diet-tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1??? ?? 0.6%??? and ??15N at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0??? ?? 1.0%??? and 7.3??? ?? 1.2??? relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8??? ?? 1.0??? change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0??? 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0??? 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts. ?? 2008 NRC.

Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

PubMed

Balaban, Noa; Bernstein, Anat; Gelman, Faina; Ronen, Zeev

2016-08-01

In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed. Biodegradation under aerobic conditions was accompanied by a significant carbon isotope effect with an isotopic enrichment factor of ɛCbulk = -8.8‰ ± 1.5‰, without any detectable bromine isotope fractionation. It was found that molecular oxygen is necessary for biodegradation to occur, suggesting an initial oxidative step. Based on these results, it was proposed that H abstraction from the C-H bond is the first step of TBNPA biodegradation under aerobic conditions, and that the C-H bond cleavage results in the formation of unstable intermediates, which are rapidly debrominated. A preliminary isotopic analysis of TBNPA in the groundwater underlying the industrial area revealed that there are no changes in the carbon and bromine isotope ratio values downstream of the contamination source. Considering that anoxic conditions prevail in the groundwater of the contaminated site, the lack of isotope shifts in TBNPA indicates the lack of TBNPA biodegradation in the groundwater, in accordance with our findings. Copyright © 2016 Elsevier Ltd. All rights reserved.

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

USGS Publications Warehouse

Burruss, R.C.; Laughrey, C.D.

2010-01-01

During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

CALUTRON RECEIVER

DOEpatents

Barnes, S.W.

1959-08-25

An improvement in a calutron receiver for collecting the isotopes ts described. The electromagnetic separation of the isotopes produces a mass spectrum of closely adjacent beams of ions at the foci regions, and a dividing wall between the two pockets is arranged at an angle. Substantially all of the tons of the less abundant isotope enter one of the pockets and strike one side of the wall directly, while substantially none of the tons entering the other pocket strikes the wall directly.

STELLAR ORIGINS OF EXTREMELY {sup 13}C- AND {sup 15}N-ENRICHED PRESOLAR SIC GRAINS: NOVAE OR SUPERNOVAE?

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

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.

Extreme excesses of {sup 13}C ({sup 12}C/{sup 13}C < 10) and {sup 15}N ({sup 14}N/{sup 15}N < 20) in rare presolar SiC grains have been considered diagnostic of an origin in classical novae, though an origin in core collapse supernovae (CCSNe) has also been proposed. We report C, N, and Si isotope data for 14 submicron- to micron-sized {sup 13}C- and {sup 15}N-enriched presolar SiC grains ({sup 12}C/{sup 13}C < 16 and {sup 14}N/{sup 15}N < ∼100) from Murchison, and their correlated Mg–Al, S, and Ca–Ti isotope data when available. These grains are enriched in {sup 13}C and {sup 15}N,more » but with quite diverse Si isotopic signatures. Four grains with {sup 29,30}Si excesses similar to those of type C SiC grains likely came from CCSNe, which experienced explosive H burning occurred during explosions. The independent coexistence of proton- and neutron-capture isotopic signatures in these grains strongly supports heterogeneous H ingestion into the He shell in pre-supernovae. Two of the seven putative nova grains with {sup 30}Si excesses and {sup 29}Si depletions show lower-than-solar {sup 34}S/{sup 32}S ratios that cannot be explained by classical nova nucleosynthetic models. We discuss these signatures within the CCSN scenario. For the remaining five putative nova grains, both nova and supernova origins are viable because explosive H burning in the two stellar sites could result in quite similar proton-capture isotopic signatures. Three of the grains are sub-type AB grains that are also {sup 13}C enriched, but have a range of higher {sup 14}N/{sup 15}N. We found that {sup 15}N-enriched AB grains (∼50 < {sup 14}N/{sup 15}N < ∼100) have distinctive isotopic signatures compared to putative nova grains, such as higher {sup 14}N/{sup 15}N, lower {sup 26}Al/{sup 27}Al, and lack of {sup 30}Si excess, indicating weaker proton-capture nucleosynthetic environments.« less

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Romanek, C.; Gibson, E.; Socki, R.; Burkett, P. J.

1993-07-01

Heretofore unresolved micrometer-scale carbon isotopic zonation in the Murchison meteorite (CM3) is documented using a laser microprobe mass spectrometer. High-resolution isotopic gradients and heterogeneities between high- and low-temperature textural components help to constrain the processes that have shaped the physiochemical character of this carbonaceous chondrite. Previous bulk samples of Murchison yield an average delta ^13C value of - 5.7 +/- 4.3 per mil [1] while individual components such as micrometer-sized mineral separates (e.g., C(sub)graphite , C(sub)diamond, and SiC), acid- soluble extracts (e.g., CaCO3 and polar hydrocarbons), and insoluble residues (e.g., polycyclic aromatic hydrocarbons) are isotopically diverse (delta ^13C of -1000 to 29,000 per mil). While these studies shed light on the origin and occurrence of C-bearing phases, they fail to constrain intrinsic spatial isotopic heterogeneities. The power of the laser microprobe lies in the fact that in situ chemical and isotopic compositions are measured simultaneously for volatiles extracted from extremely small sample volumes (i.e., 0.025 mm^3 for 5 wt% C). Nd-YAG laser irradiation (1.06 micrometers) is directed onto texturally defined targets (>=50 micrometers wide) from which solid material is volatilized. Condensible gaseous phases are collected in a variable-temperature cold trap while the more volatile species (CH4 and CO) are quantified using an ion trap mass spectrometer. All gases are then converted to CO2 in a CuO furnace (containing Pt) held at 600 degrees C and analyzed for carbon and oxygen isotope ratios. The concentration and isotopic composition of condensed species are determined by stepped sublimation of unstable components and conversion to CO2. Preliminary isotopic analyses of the total volatile C content (i.e., bulk microanalysis) from distinct textural components at least 0.05 mm^3 in volume are described below. The most ^13C-depleted components within Murchison reside within the cores of chondrules and/or aggregates. Three typical cores were analyzed, with an average bulk composition of -21.0 +/- 0.5 per mil (n = 7). The bulk ^13C content of C-bearing phases increases monotonically outward in all directions within 100 to 200 micrometers of each core (i.e., within dust mantles) to a constant matrix value of -12.5 +/- 0.5 per mil (n = 40). The most isotopically enriched textural component found in Murchison is a regolith breccia clast without chondrules that has an average bulk delta ^13C value of -10 +/-0.5 per mil (n = 5). The clast was originally detectable only under cathodoluminescence, but with the aid of the laser microprobe it is now characterized by an unusually low volatile content and enriched ^13C composition. In general, the most isotopically enriched components also produce the lowest yield of gas (normalized to sampling volume). This trend of isotopic enrichment from chondrule to matrix has been documented previously for oxygen isotopes in carbonaceous chondrites [2]. Carbon isotopic gradients and heterogeneities within Murchison reflect fundamental changes in the chemical speciation and/or isotopic content of the main C-bearing components (i.e., acid-soluble and insoluble hydrocarbon fractions) within the meteorite. Perhaps core interiors and dust mantles are responding to environmental changes reflected in the speciation of C-bearing species distributed within the solar nebula or the parent body. Inverse correlations between hydrocarbon atomic mass number and ^13C abundance in the acid-soluble [3] and insoluble residues [4] of Murchison have been documented. Alternatively, micrometer-scale isotopic gradients may reflect fundamental changes in the isotopic composition of individual C-bearing species through time. Enrichments may represent kinetically controlled processes related to hydrocarbon formation. In contrast, assuming an equilibrium fractionation mechanism, isotopic enrichments may record a temperature-dependent component to hydrocarbon delta ^13C values. These opposing alternatives will be discussed in light of the isotopic composition of individual C-bearing components volatilized from tightly constrained sample volumes within Murchison. References: [1] Kerridge J. F. (1985) GCA, 49, 1707-1714. [2] Clayton R. N. and Mayeda T. K. (1984) EPSL, 67, 151-161. [3] Yuen G. et al. (1984) Nature, 307, 254. [4] Gilmour I. et al. (1991) Meteoritics, 26, 337-338.

Light Stable Isotopic Compositions of Enriched Mantle Sources: Resolving the Dehydration Paradox

NASA Astrophysics Data System (ADS)

Dixon, J. E.; Bindeman, I. N.; Kingsley, R. H.

2017-12-01

An outstanding puzzle in mantle geochemistry has been the origin and evolution of Earth's volatile components. The "dehydration paradox" refers to the following conundrum. Mantle compositions for some enriched mid-ocean ridge (MORB) and ocean island (OIB) basalts basalts require involvement of a mostly dehydrated slab component to explain the trace element ratios and radiogenic isotopic compositions, but a fully hydrated slab component to explain the stable isotopic compositions. Volatile and stable isotopic data on enriched MORB show a diversity of enriched components. Pacific PREMA-type basalts (H2O/Ce = 215 ± 30, δDSMOW = -45 ± 5 ‰) are similar to those in the north Atlantic (H2O/Ce = 220 ± 30; δDSMOW = -30 to -40 ‰). Basalts with EM-type signatures have regionally variable volatile compositions. North Atlantic EM-type basalts are wetter (H2O/Ce = 330 ± 30) and have isotopically heavier hydrogen (δDSMOW = -57 ± 5 ‰) than north Atlantic MORB. South Atlantic EM-type basalts are damp (H2O/Ce = 120 ± 10) with intermediate δDSMOW (-68 ± 2 ‰), similar to dDSMOW for Pacific MORB. North EPR EM-type basalts are dry (H2O/Ce = 110 ± 20) and isotopically light (δDSMOW = -94 ± 3 ‰). Boron and lithium isotopic ratios parallel the trends observed for dDSMOW. A multi-stage metasomatic and melting model accounts for the origin of the enriched components by extending the subduction factory concept down through the mantle transition zone, with slab temperature a key variable. The dehydration paradox is resolved by decoupling of volatiles from lithophile elements, reflecting primary dehydration of the slab followed by secondary rehydration and re-equilibration by fluids derived from subcrustal hydrous phases (e.g., antigorite) in cooler, deeper parts of the slab. The "expanded subduction factory" model includes melting at several key depths, including 1) 180 to 280 km, where EM-type mantle compositions are generated above slabs with average to hot thermal profiles by addition of <1% carbonated sediment-derived supercritical fluids/melts to depleted asthenospheric or subcontinental lithospheric mantle, and 2) 410 to 660 km, where PREMA-type mantle sources are generated, above slabs with average to cool thermal profiles, by addition of <1% carbonated eclogite ± sediment-derived supercritical fluids to depleted mantle.

Toward a better δDalkanes paleoclimate proxy; Partitioning of seasonal water sources and xylem-leaf deuterium enrichment according to plant growth form and phenology

NASA Astrophysics Data System (ADS)

Wispelaere, Lien; Bodé, Samuel; Herve-Fernández, Pedro; Hemp, Andreas; Verschuren, Dirk; Boeckx, Pascal

2016-04-01

The DeepCHALLA consortium is preparing an ICDP (International Continental Drilling Program) deep-drilling project on Lake Challa, a crater lake near Mt. Kilimanjaro in equatorial East Africa, where the climate is tropical semi-arid climate and characterized by two distinct rainy seasons. The main objective of this project is to acquire high-resolution and accurately dated proxy data of continental climate and ecosystem change near the Equator over 250,000 years. One of the paleoclimate proxies to be used is the hydrogen-isotopic composition of sedimentary n-alkanes (δDalkanes) derived from fossil plant leaf wax. However, this requires a better understanding of seasonal variability in the isotopic composition of precipitation, and of the fractionation of its hydrogen during incorporation in the plant waxes. In addition, recent studies have described the existence of "two water worlds", resulting in an additional deviation of the isotopic composition of the water taken up by plants. In this study, we measured the δD and δ18O of local precipitation, lake water, and xylem and leaf water from different plant species, seasons and sites with varying distances to Lake Challa. We use these data to set up a local meteoric water line (LMWL), and to assess spatial and temporal patterns of water utilization by local plants. Our data show a seasonal change in water-isotope partitioning with plants tapping water from isotopically lighter water sources during the dry seasons, as indicated by more negative xylem δD values and higher offsets from precipitation (i.e. greater distances from the LMWL), therefore supporting the "two water worlds" hypothesis. Surprisingly, trees appear to preferentially exploit isotopically more enriched sources of soil water, suggesting shallower water sources, than shrubs. Plants located at the lake shore use a mixture of precipitation and lake water, reflected in enriched xylem δD values and in the intersection of 2H and 18O with the LMWL. Leaf-water deuterium enrichment, averaged over all plant species, sites and seasons equals 23 ± 27‰. Several factors influence the isotopic enrichment between xylem and leaf water, but according to our results, the growth form and phenology of plant species are the primary factors, while the location (proximity to the lake) and season exert relatively minor effects.

Isotopic evidence of early hominin diets

NASA Astrophysics Data System (ADS)

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.

Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

PubMed

Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

2014-11-18

We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

Isotopic evidence of early hominin diets

PubMed Central

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

2013-01-01

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.

Isotope Mixes, Corresponding Nuclear Properties and Reactor Design Implications of Naturally Occurring Lead Sources

DTIC Science & Technology

2013-06-01

39  Table 8.  Required enrichment for criticality ...keff ~ 1)-1. ...............................................44  Table 9.  Required enrichment for criticality (keff ~ 1)-2...45  Table 10.  Required enrichment for SSTAR based model reactor to achieve criticality using various natural lead concentrations

Protein expression and isotopic enrichment based on induction of the Entner-Doudoroff pathway in Escherichia coli

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

Refaeli, Bosmat; Goldbourt, Amir, E-mail: amirgo@post.tau.ac.il

2012-10-12

Highlights: Black-Right-Pointing-Pointer The Entner-Doudoroff pathway is induced during protein expression in E. coli. Black-Right-Pointing-Pointer 1-{sup 13}C-gluconate and {sup 15}NH{sub 4}Cl provide a carbonyl-amide protein backbone labeling scheme. Black-Right-Pointing-Pointer The enrichment pattern is determined by nuclear magnetic resonance. -- Abstract: The Entner-Doudoroff pathway is known to exist in many organisms including bacteria, archea and eukarya. Although the common route for carbon catabolism in Escherichia coli is the Embden-Meyerhof-Parnas pathway, it was shown that gluconate catabolism in E. coli occurs via the Entner-Doudoroff pathway. We demonstrate here that by supplying BL21(DE3) competent E.coli cells with gluconate in a minimal growth medium, proteinmore » expression can be induced. Nuclear magnetic resonance data of over-expressed ubiquitin show that by using [1-{sup 13}C]-gluconate as the only carbon source, and {sup 15}N-enriched ammonium chloride, sparse isotopic enrichment in the form of a spin-pair carbonyl-amide backbone enrichment is obtained. The specific amino acid labeling pattern is analyzed and is shown to be compatible with Entner-Doudoroff metabolism. Isotopic enrichment serves as a key factor in the biophysical characterization of proteins by various methods including nuclear magnetic resonance, mass spectrometry, infrared spectroscopy and more. Therefore, the method presented here can be applied to study proteins by obtaining sparse enrichment schemes that are not based on the regular glycolytic pathway, or to study the Entner-Doudoroff metabolism during protein expression.« less

Food webs of two intermittently open estuaries receiving 15N-enriched sewage effluent

NASA Astrophysics Data System (ADS)

Hadwen, Wade L.; Arthington, Angela H.

2007-01-01

Carbon and nitrogen stable isotope signatures were used to assess the response of food webs to sewage effluent discharged into two small intermittently open estuaries in northern New South Wales, Australia. One of these systems, Tallows Creek, has a history of direct sewage inputs, whilst the other, Belongil Creek, receives wastewater via an extensive wetland treatment system. The food webs of both systems were driven by algal sources of carbon, reflecting high autotrophic productivity in response to the nutrients entering the system from sewage effluent. All aquatic biota collected from Tallows Creek had significantly enriched δ15N signatures relative to their conspecifics from Belongil Creek, indicating that sewage nitrogen had been assimilated and transferred throughout the Tallows Creek food web. These δ15N values were higher than those reported from studies in permanently open estuaries receiving sewage effluent. We suggest that these enriched signatures and the transfer of nitrogen throughout the entire food web reflect differences in hydrology and associated nitrogen cycling processes between permanently open and intermittently open estuaries. Although all organisms in Tallows Creek were generally 15N-enriched, isotopically light (less 15N-enriched) individuals of estuary perchlet ( Ambassis marianus) and sea mullet ( Mugil cephalus) were also collected. These individuals were most likely recent immigrants into Tallows Creek, as this system had only recently been opened to the ocean. This isotopic discrimination between resident (enriched) and immigrant (significantly less enriched) individuals can provide information on fish movement patterns and the role of heavily polluted intermittently open estuaries in supporting commercially and recreationally valuable estuarine species.

Constraints on Nucleosynthesis from Xenon Isotopes in Presolar Material

NASA Astrophysics Data System (ADS)

Gilmour, J. D.; Turner, G.

2007-03-01

By applying theoretical constraints to three-dimensional fits of xenon isotope data from presolar grains, we show that they strongly suggest a nucleosynthesis process that produces ``r-process'' isotopes without producing s-process isotopes (128Xe, 130Xe) and without producing the conventional r-process isotope 136Xe. It is one of three distinct nucleosynthetic sources that are necessary and sufficient to explain the gross variation in xenon isotopic data across all presolar material. The other source contributing r-process isotopes is responsible for the heavy isotope signature identified in nanodiamonds, which is also present in presolar SiC, and is associated with light isotope enrichment. The relative enrichments of heavy and light isotopes in this component in nanodiamonds and SiC grains are different, implying that the parent nucleosynthetic processes are not inextricably linked. Because minor variations in the isotopic compositions of xenon trapped in nanodiamonds show that two distinct sites contributed nanodiamonds to the early solar system within the average grain lifetime, it is suggested that Type IIa supernovae (SNe IIa) are not the source of the nanodiamonds. The s-process signature derived is consistent with that derived from mixing lines between grain subpopulations for isotopes on the s-process path. This implies that a pure end-member is present in the grains (although not approached in analyses). Our approach is more general and provides a less restrictive set of numerical constraints to be satisfied by proposed theoretical treatments of nucleosynthesis.

Utilization of non-weapons-grade plutonium and highly enriched uranium with breeding of the {sup 233}U isotope in the VVER reactors using thorium and heavy water

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

Marshalkin, V. E., E-mail: marshalkin@vniief.ru; Povyshev, V. M.

A method for joint utilization of non-weapons-grade plutonium and highly enriched uranium in the thorium–uranium—plutonium oxide fuel of a water-moderated reactor with a varying water composition (D{sub 2}O, H{sub 2}O) is proposed. The method is characterized by efficient breeding of the {sup 233}U isotope and safe reactor operation and is comparatively simple to implement.

Effect of plastic deformation on the magnetic properties and dislocation luminescence of isotopically enriched silicon {sup 29}Si:B

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

Koplak, O. V.; Shteynman, E. A.; Tereschenko, A. N.

2015-09-15

A correlation between the temperature dependences of the D1-line intensity of dislocation luminescence and the magnetic moment of plastically deformed isotopically enriched crystals {sup 29}Si:B is found. It is established that the magnetic susceptibility of the deformed crystals obtained by integration of the spectra of electron spin resonance and the D1-line intensity undergo similar nonmonotonic variations with temperature varying in the range of 20–32 K.

The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

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

Liezers, Martin; Farmer, Orville T.; Dion, Michael P.

2015-01-01

We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recoverymore » of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.« less

Axi-symmetrical flow reactor for [sup 196]Hg photochemical enrichment

DOEpatents

Grossman, M.W.

1991-04-30

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, [sup 196]Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired [sup 196]Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith. 10 figures.

Summary of the Effort to Use Active-induced Time Correlation Techniques to Measure the Enrichment of HEU

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

McConchie, Seth M.; Crye, Jason Michael; Pena, Kirsten

2015-09-30

This document summarizes the effort to use active-induced time correlation techniques to measure the enrichment of bulk quantities of enriched uranium. In summary, these techniques use an external source to initiate fission chains, and the time distribution of the detected fission chain neutrons is sensitive to the fissile material enrichment. The number of neutrons emitted from a chain is driven by the multiplication of the item, and the enrichment is closely coupled to the multiplication of the item. As the enrichment increases (decreases), the multiplication increases (decreases) if the geometry is held constant. The time distribution of fission chain neutronsmore » is a complex function of the enrichment and material configuration. The enrichment contributes to the probability of a subsequent fission in a chain via the likelihood of fissioning on an even-numbered isotope versus an odd-numbered isotope. The material configuration contributes to the same probability via solid angle effects for neutrons inducing subsequent fissions and the presence of any moderating material. To simplify the ability to accurately measure the enrichment, an associated particle imaging (API) D-T neutron generator and an array of plastic scintillators are used to simultaneously image the item and detect the fission chain neutrons. The image is used to significantly limit the space of enrichment and material configuration and enable the enrichment to be determined unambiguously.« less

Isotopic composition of transpiration and rates of change in leaf water isotopologue storage in response to environmental variables.

PubMed

Simonin, Kevin A; Roddy, Adam B; Link, Percy; Apodaca, Randy; Tu, Kevin P; Hu, Jia; Dawson, Todd E; Barbour, Margaret M

2013-12-01

During daylight hours, the isotope composition of leaf water generally approximates steady-state leaf water isotope enrichment model predictions. However, until very recently there was little direct confirmation that isotopic steady-state (ISS) transpiration in fact exists. Using isotope ratio infrared spectroscopy (IRIS) and leaf gas exchange systems we evaluated the isotope composition of transpiration and the rate of change in leaf water isotopologue storage (isostorage) when leaves were exposed to variable environments. In doing so, we developed a method for controlling the absolute humidity entering the gas exchange cuvette for a wide range of concentrations without changing the isotope composition of water vapour. The measurement system allowed estimation of (18)O enrichment both at the evaporation site and for bulk leaf water, in the steady state and the non-steady state. We show that non-steady-state effects dominate the transpiration isoflux even when leaves are at physiological steady state. Our results suggest that a variable environment likely prevents ISS transpiration from being achieved and that this effect may be exacerbated by lengthy leaf water turnover times due to high leaf water contents. © 2013 John Wiley & Sons Ltd.

Pythons metabolize prey to fuel the response to feeding.

PubMed Central

Starck, J. Matthias; Moser, Patrick; Werner, Roland A.; Linke, Petra

2004-01-01

We investigated the energy source fuelling the post-feeding metabolic upregulation (specific dynamic action, SDA) in pythons (Python regius). Our goal was to distinguish between two alternatives: (i) snakes fuel SDA by metabolizing energy depots from their tissues; or (ii) snakes fuel SDA by metabolizing their prey. To characterize the postprandial response of pythons we used transcutaneous ultrasonography to measure organ-size changes and respirometry to record oxygen consumption. To discriminate unequivocally between the two hypotheses, we enriched mice (= prey) with the stable isotope of carbon (13C). For two weeks after feeding we quantified the CO2 exhaled by pythons and determined its isotopic 13C/12C signature. Ultrasonography and respirometry showed typical postprandial responses in pythons. After feeding, the isotope ratio of the exhaled breath changed rapidly to values that characterized enriched mouse tissue, followed by a very slow change towards less enriched values over a period of two weeks after feeding. We conclude that pythons metabolize their prey to fuel SDA. The slowly declining delta13C values indicate that less enriched tissues (bone, cartilage and collagen) from the mouse become available after several days of digestion. PMID:15255044

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

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

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

Lead isotopes and trace metals in dust at Yucca Mountain

USGS Publications Warehouse

Kwak, Loretta; Neymark, Leonid A.; Peterman, Zell E.

2008-01-01

Lead (Pb)-isotope compositions and trace-metal concentrations were determined for samples of dust collected from underground and surface locations at and near the proposed radioactive waste repository at Yucca Mountain, Nevada. Rare earth element concentrations in the dust samples from the underground tunnels are similar to those in wholerock samples of the repository host rocks (Miocene Tiva Canyon Tuff and Topopah Spring Tuff), supporting interpretation that the subsurface dust is mainly composed of rock comminuted during tunnel construction. Other trace metals (arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead, antimony, thallium, and zinc) are variably enriched in the subsurface dust samples relative to the average concentrations in the host rocks. Average concentrations of arsenic and lead in dust samples, high concentrations of which can cause corrosion of waste canisters, have enrichment factors from 1.2 to 1.6 and are insignificant relative to the range of concentrations for these metals observed in the host rock samples. Most dust samples from surface sites also are enriched in many of these trace metals relative to average repository host rocks. At least some of these enrichments may be artifacts of sampling. Plotted on a 208Pb/206Pb-207Pb/206Pb graph, Pb-isotope compositions of dust samples from underground sites form a mixing line extending from host-rock Pb-isotope compositions towards compositions of many of the dust samples from surface sites; however, combined Pb concentration and isotope data indicate the presence of a Pbenriched component in the subsurface dust that is not derived from host rock or surface dust and may derive from anthropogenic materials introduced into the underground environment.

Silicon Isotope Geochemistry of Ocean Island Basalts: Mantle Heterogeneities and Contribution of Recycled Oceanic Crust and Lithosphere

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.

2015-12-01

The study of Silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to elucidate between possible heterogeneities in the mantle. Relatively large (~several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1]. In contrast, only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed in high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material (derived from low-temperature surface processes) in OIB source regions in a manner similar to more conventional stable isotope systems, such as O. Here we present the first comprehensive set of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIBs, including new data for the Canary Islands. Samples represent the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. Average δ30Si values for OIBs representing the EM-1 (-0.32 ± 0.06‰, 2 sd), EM-2 (-0.30 ± 0.01‰, 2 sd), and HIMU (-0.34 ± 0.09‰, 2 sd) mantle components are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth [3]. However, small systematic variations are present; HIMU (Mangaia, Cape Verde, La Palma) and Iceland OIBs are enriched in the lighter isotopes of Si (δ30Si values lower than MORB). Further, the difference in Si isotope composition between La Palma and El Heirro (Canary Islands) has previously been observed for O isotopes [4], suggesting a relationship between the Si and O isotope mantle systematics. The Si isotope variations among OIBs may be explained by the sampling of a primitive mantle reservoir enriched in the light isotopes of Si, as suggested by [5], but most likely reflects the incorporation of recycled altered oceanic crust and lithosphere in the plume source. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Day et al., Geology 2009 [5] Huang et al., GCA 2014

Pathways of CH3Hg and Hg Ingestion in Benthic Organisms: An Enriched Isotope Approach

PubMed Central

2015-01-01

Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg+ and Hg2+, into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg+ and Hg2+ uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg+ or Hg2+ were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg2+ occurred during the course of the experiment, enhancing the uptake of Hg2+ spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments. PMID:24678910

Pathways of CH3Hg and Hg ingestion in benthic organisms: an enriched isotope approach.

PubMed

Taylor, Vivien F; Bugge, Deenie; Jackson, Brian P; Chen, Celia Y

2014-05-06

Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg(+) and Hg(2+), into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg(+) and Hg(2+) uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg(+) or Hg(2+) were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg(2+) occurred during the course of the experiment, enhancing the uptake of Hg(2+) spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments.

Hybrid isotope separation scheme

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus.

Fundamental studies in isotope chemistry. Progress report, 1 August 1982-1 August 1983

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

Bigeleisen, J.

1983-01-01

Interest in a search for superheavy elements present in nature as a remnant of the big bang or through continuous production by cosmic rays has prompted us to study the isotope chemistry of superheavy elements. Calculations of the fractionation factors of superheavy elements of masses 10, 100, 1000, and in the form of isotopes of hydrogen, carbon, selenium and uranium against the light naturally occurring isotope of the element show that the superheavy isotope, even of infinite mass, will not be sufficiently fractionated in single stage natural processes to obscure its chemistry. Calculations have been made of the elementary separationmore » factors of superheavy isotopes of carbon and oxygen by fractional distillation of CO at 80/sup 0/K. The fractionation factors are discussed in terms of a model for liquid CO in good agreement with experimental data on /sup 13/C/sup 16/O and /sup 12/C/sup 18/O. Calculations for very heavy isotopic forms of CO reveal for the first time the coupling effect between translation and internal vibration in the liquid. It is shown that a 1ow temperature distillation plant, such as the Los Alamos COLA plant, has a significant potential for enrichment of superheavy isotopes of carbon. The maximum enrichment factor is 10/sup 55/.« less

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

PubMed

Baune, Claudia; Bottcher, Michael E

2010-12-01

The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H₂S(aq) to the gaseous phase. The assumption of pure physical outgassing of H₂S(aq) at low pH values leads to an isotope enrichment factor of -0.9 ± 0.4‰ (n = 14) which is caused by the combined differences in dehydration and diffusion coefficients of H₂³²S(aq) and H₂³⁴S(aq). In the pH range of natural surface and shallow pore waters, ³⁴S will be equal to or enriched in the gaseous phase compared to the aqueous solution, therefore creating no or a slight enrichment of ³²S in the aqueous solution. Experiments in seawater solution showed no significant influence of increased ionic strength and changed corresponding aqueous speciation on sulphur isotope effects.

Differing source water inputs, moderated by evaporative enrichment, determine the contrasting δ18OCELLULOSE signals in maritime Antarctic moss peat banks

NASA Astrophysics Data System (ADS)

Royles, Jessica; Sime, Louise C.; Hodgson, Dominic A.; Convey, Peter; Griffiths, Howard

2013-03-01

Oxygen isotope palaeoclimate records, preserved in moss tissue cellulose, are complicated by environmental influences on the relationships between source water inputs and evaporative conditions. We carried out stable isotope analyses of precipitation collected from the maritime Antarctic and cellulose extracted from co-located Chorisodontium aciphyllum dominated moss peat bank deposits accumulated since 1870 A.D. Analyses of stable oxygen and hydrogen isotope composition of summer precipitation on Signy Island (60.7°S, 45.6°W) established a local meteoric water line (LMWL) similar to both the global MWL and other LMWLs, and almost identical to the HadAM3 isotope-enabled global circulation model output. The oxygen isotopic composition of cellulose (δ18OC) revealed little temporal variation between four moss peat banks on Signy Island since 1870. However, δ18OC followed two patterns with Sites A and D consistently 3‰ enriched relative to δ18OC values from Sites B and C. The growing moss surfaces at Sites A and D are likely to have been hydrated by isotopically heavier summer precipitation, whilst at Sites B and C, the moss banks are regularly saturated by the isotopically depleted snow melt streams. Laboratory experiments revealed that evaporative enrichment of C. aciphyllum moss leaf water by 5‰ occurred rapidly following saturation (ecologically equivalent to post-rainfall or snow melt periods). In addition to the recognized source water-cellulose fractionation extent of 27 ± 3‰, such a shift would account for the 32‰ difference measured between δ18O of Signy Island precipitation and cellulose.

Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

NASA Astrophysics Data System (ADS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-09-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Plant family identity distinguishes patterns of carbon and nitrogen stable isotope abundance and nitrogen concentration in mycoheterotrophic plants associated with ectomycorrhizal fungi

PubMed Central

Hynson, Nicole A.; Schiebold, Julienne M.-I.; Gebauer, Gerhard

2016-01-01

Background and Aims Mycoheterotrophy entails plants meeting all or a portion of their carbon (C) demands via symbiotic interactions with root-inhabiting mycorrhizal fungi. Ecophysiological traits of mycoheterotrophs, such as their C stable isotope abundances, strongly correlate with the degree of species’ dependency on fungal C gains relative to C gains via photosynthesis. Less explored is the relationship between plant evolutionary history and mycoheterotrophic plant ecophysiology. We hypothesized that the C and nitrogen (N) stable isotope compositions, and N concentrations of fully and partially mycoheterotrophic species differentiate them from autotrophs, and that plant family identity would be an additional and significant explanatory factor for differences in these traits among species. We focused on mycoheterotrophic species that associate with ectomycorrhizal fungi from plant families Ericaceae and Orchidaceae. Methods Published and unpublished data were compiled on the N concentrations, C and N stable isotope abundances (δ13C and δ15N) of fully (n = 18) and partially (n = 22) mycoheterotrophic species from each plant family as well as corresponding autotrophic reference species (n = 156). These data were used to calculate site-independent C and N stable isotope enrichment factors (ε). Then we tested for differences in N concentration, 13C and 15N enrichment among plant families and trophic strategies. Key Results We found that in addition to differentiating partially and fully mycoheterotrophic species from each other and from autotrophs, C and N stable isotope enrichment also differentiates plant species based on familial identity. Differences in N concentrations clustered at the plant family level rather than the degree of dependency on mycoheterotrophy. Conclusions We posit that differences in stable isotope composition and N concentrations are related to plant family-specific physiological interactions with fungi and their environments. PMID:27451987

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

A novel membrane inlet mass spectrometer method to measure ¹⁵NH4₄⁺ for isotope-enrichment experiments in aquatic ecosystems.

PubMed

Yin, Guoyu; Hou, Lijun; Liu, Min; Liu, Zhanfei; Gardner, Wayne S

2014-08-19

Nitrogen (N) pollution in aquatic ecosystems has attracted much attention over the past decades, but the dynamics of this bioreactive element are difficult to measure in aquatic oxygen-transition environments. Nitrogen-transformation experiments often require measurement of (15)N-ammonium ((15)NH4(+)) ratios in small-volume (15)N-enriched samples. Published methods to determine N isotope ratios of dissolved ammonium require large samples and/or costly equipment and effort. We present a novel ("OX/MIMS") method to determine N isotope ratios for (15)NH4(+) in experimental waters previously enriched with (15)N compounds. Dissolved reduced (15)N (dominated by (15)NH4(+)) is oxidized with hypobromite iodine to nitrogen gas ((29)N2 and/or (30)N2) and analyzed by membrane inlet mass spectrometry (MIMS) to quantify (15)NH4(+) concentrations. The N isotope ratios, obtained by comparing the (15)NH4(+) to total ammonium (via autoanalyzer) concentrations, are compared to the ratios of prepared standards. The OX/MIMS method requires only small sample volumes of water (ca. 12 mL) or sediment slurries and is rapid, convenient, accurate, and precise (R(2) = 0.9994, p < 0.0001) over a range of salinities and (15)N/(14)N ratios. It can provide data needed to quantify rates of ammonium regeneration, potential ammonium uptake, and dissimilatory nitrate reduction to ammonium (DNRA). Isotope ratio results agreed closely (R = 0.998, P = 0.001) with those determined independently by isotope ratio mass spectrometry for DNRA measurements or by ammonium isotope retention time shift liquid chromatography for water-column N-cycling experiments. Application of OX/MIMS should simplify experimental approaches and improve understanding of N-cycling rates and fate in a variety of freshwater and marine environments.

Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

NASA Astrophysics Data System (ADS)

Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

2016-06-01

We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

Illuminating hydrological processes at the soil-vegetation-atmosphere interface with water stable isotopes

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Leistert, Hannes; Gimbel, Katharina; Weiler, Markus

2016-09-01

Water stable isotopes (18O and 2H) are widely used as ideal tracers to track water through the soil and to separate evaporation from transpiration. Due to the technical developments in the last two decades, soil water stable isotope data have become easier to collect. Thus, the application of isotope methods in soils is growing rapidly. Studies that make use of soil water stable isotopes often have a multidisciplinary character since an interplay of processes that take place in the vadose zone has to be considered. In this review, we provide an overview of the hydrological processes that alter the soil water stable isotopic composition and present studies utilizing pore water stable isotopes. The processes that are discussed include the water input as precipitation or throughfall, the output as evaporation, transpiration, or recharge, and specific flow and transport processes. Based on the review and supported by additional data and modeling results, we pose a different view on the recently proposed two water world hypothesis. As an alternative to two distinct pools of soil water, where one pool is enriched in heavy isotopes and used by the vegetation and the other pool does not undergo isotopic fractionation and becomes recharge, the water gets successively mixed with newly introduced rainwater during the percolation process. This way, water initially isotopically enriched in the topsoil loses the fractionation signal with increasing infiltration depth, leading to unfractionated isotopic signals in the groundwater.

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

NASA Astrophysics Data System (ADS)

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

2005-09-01

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

Precession and glacial-cycle controls of monsoon precipitation isotope changes over East Asia during the Pleistocene

NASA Astrophysics Data System (ADS)

Huang, Enqing; Chen, Yunru; Schefuß, Enno; Steinke, Stephan; Liu, Jingjing; Tian, Jun; Martínez-Méndez, Gema; Mohtadi, Mahyar

2018-07-01

Precipitation isotope reconstructions derived from speleothems and plant waxes are important archives for understanding hydroclimate dynamics. Their climatic significance in East Asia, however, remains controversial. Here we present terrestrial plant-wax stable hydrogen isotope (δDwax) records over periods covering the last four interglacials and glacial terminations from sediment cores recovered from the northern South China Sea (SCS) as an archive of regionally-integrated precipitation isotope changes in Southeast China. Combined with previous precipitation isotope reconstructions from China, we find that the SCS δDwax and Southwest-Central China stalagmite δ18O records show relatively enriched and depleted isotopic values, respectively, during interglacial peaks; but relatively similar isotopic variations during most sub-interglacials and glacial periods over the past 430 thousand years. During interglacial peaks, strong summer insolation should have intensified the convection intensity, the isotopic fractionation along moisture trajectories and the seasonality, which are all in favor of causing isotopically-depleted rainfall over the East Asian monsoon regime. These effects in combination with a relatively high proportion of Indian Ocean- versus Pacific-sourced moisture influx should have resulted in strongly depleted precipitation isotopes (stalagmite δ18O) over most parts of China. However, Southeast China should have been affected by a relatively low ratio of Indian Ocean- versus Pacific-sourced moisture influx, which dominated over effects yielding depleted precipitation isotopes and led to enriched precipitation isotopes (δDwax). It is thus concluded that glacial boundary conditions and insolation forcing are the two most important factors for causing regional differences in precipitation isotope compositions over subtropical East Asia on orbital timescales.

The Isotopic Record From Monogenetic Seamounts: Insights Into Recycling Time Scales In The Upper Mantle

NASA Astrophysics Data System (ADS)

Madrigal Quesada, P.; Gazel, E.

2017-12-01

Monogenetic seamounts related to non-plume intraplate magmatism provide a window into the composition of upper mantle heterogeneities, nevertheless, the origin of these heterogeneities are still not well constrained. Radiogenic isotopes (Sr-Nd-Pb) from present-day ocean island basalts (OIB) produced by this type of magmatism can help establish the source compositions of these chemically and isotopically enriched reservoirs. Here we present evidence that suggests that a highly enriched mantle reservoir can originate from OIB-type subducted material that gets incorporated and stirred throughout the upper mantle. We explore this hypothesis using data from non-plume related OIB volcanism; focusing on isolated monogenetic seamounts with no apparent age progression and interpreted to be related to either plate flexure, shear driven convection and/or edge convection. The isotopic record compiled, added to new results obtained from accreted petit-spot seamounts from Santa Elena Peninsula in Costa Rica, suggest that a highly radiogenic mantle reservoir originated from recycled seamount materials can be formed in a shorter time scale than ancient subducted oceanic crust (>1 Ga), thought to be the forming agent of the HIMU mantle "flavor" found in some of these small-scale seamounts. The implications of these results entail that the recycling of already enriched materials in short time scales and in restricted depths within the Upper Mantle may play an important role in the source of OIBs (plume and non-plume related), as well as, the most enriched suites of EMORBs.

Effects of trophic level and metamorphosis on discrimination of hydrogen isotopes in a plant-herbivore system

USGS Publications Warehouse

Peters, Jacob M.; Wolf, Nathan; Stricker, Craig A.; Collier, Timothy R.; Martinez del Rio, Carlos

2012-01-01

The use of stable isotopes in ecological studies requires that we know the magnitude of discrimination factors between consumer and element sources. The causes of variation in discrimination factors for carbon and nitrogen have been relatively well studied. In contrast, the discrimination factors for hydrogen have rarely been measured. We grew cabbage looper caterpillars (Trichoplusia ni) on cabbage (Brassica oleracea) plants irrigated with four treatments of deuterium-enriched water (δD = -131, -88, -48, and -2‰, respectively), allowing some of them to reach adulthood as moths. Tissue δD values of plants, caterpillars, and moths were linearly correlated with the isotopic composition of irrigation water. However, the slope of these relationships was less than 1, and hence, discrimination factors depended on the δD value of irrigation water. We hypothesize that this dependence is an artifact of growing plants in an environment with a common atmospheric δD value. Both caterpillars and moths were significantly enriched in deuterium relative to plants by ~45‰ and 23‰ respectively, but the moths had lower tissue to plant discrimination factors than did the caterpillars. If the trophic enrichment documented here is universal, δD values must be accounted for in geographic assignment studies. The isotopic value of carbon was transferred more or less faithfully across trophic levels, but δ15N values increased from plants to insects and we observed significant non-trophic 15N enrichment in the metamorphosis from larvae to adult.

Stable Carbon Isotope Fractionation in Chlorinated Ethene Degradation by Bacteria Expressing Three Toluene Oxygenases

PubMed Central

Clingenpeel, Scott R.; Moan, Jaina L.; McGrath, Danielle M.; Hungate, Bruce A.; Watwood, Mary E.

2012-01-01

One difficulty in using bioremediation at a contaminated site is demonstrating that biodegradation is actually occurring in situ. The stable isotope composition of contaminants may help with this, since they can serve as an indicator of biological activity. To use this approach it is necessary to establish how a particular biodegradation pathway affects the isotopic composition of a contaminant. This study examined bacterial strains expressing three aerobic enzymes for their effect on the 13C/12C ratio when degrading both trichloroethene (TCE) and cis-1,2-dichloroethene (c-DCE): toluene 3-monoxygenase, toluene 4-monooxygenase, and toluene 2,3-dioxygenase. We found no significant differences in fractionation among the three enzymes for either compound. Aerobic degradation of c-DCE occurred with low fractionation producing δ13C enrichment factors of −0.9 ± 0.5 to −1.2 ± 0.5, in contrast to reported anaerobic degradation δ13C enrichment factors of −14.1 to −20.4‰. Aerobic degradation of TCE resulted in δ13C enrichment factors of −11.6 ± 4.1 to −14.7 ± 3.0‰ which overlap reported δ13C enrichment factors for anaerobic TCE degradation of −2.5 to −13.8‰. The data from this study suggest that stable isotopes could serve as a diagnostic for detecting aerobic biodegradation of TCE by toluene oxygenases at contaminated sites. PMID:22363335

Sulphur isotopic ratios in mosses indicating atmospheric sulphur sources in southern Chinese mountainous areas

NASA Astrophysics Data System (ADS)

Xiao, Hua-Yun; Tang, Cong-Guo; Liu, Xue-Yan; Xiao, Hong-Wei; Liu, Cong-Qiang

2008-10-01

Many mountainous regions in South China have been confronted with the consequences of acidic deposition, but studies on atmospheric S sources are still very limited. In this study, isotopic ratios in mosses were used to discriminate atmospheric S sources. A continuous increase in S isotopic ratios was observed from the south to the north in mountainous mosses and in accord with the previously reported changing trends in urban mosses, indicating a contribution of local anthropogenic S from urban cities. Based on comparisons of S isotopic ratios in mountainous mosses with those in nearby urban mosses, we found that mountainous mosses had significantly higher 34S contents than urban mosses, especially in West China, reflecting an introduction of 34S-enriched sulphur. In conjunction with cloud water data in the literature, we concluded that 34S-enriched sulphur in northerly air masses contributed much to atmospheric S in southern Chinese mountainous areas.

37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies.

PubMed

Zakon, Yevgeni; Ronen, Zeev; Halicz, Ludwik; Gelman, Faina

2017-10-01

In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = -13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. Copyright © 2017. Published by Elsevier Ltd.

Geochemistry and mineralogy of kimberlites from the Arkhangelsk Region, NW Russia: evidence for transitional kimberlite magma types

NASA Astrophysics Data System (ADS)

Beard, A. D.; Downes, H.; Hegner, E.; Sablukov, S. M.

2000-03-01

The Arkhangelsk kimberlite province (AKP) is situated in the north of the Baltic Shield within the buried southeastern portion of the Kola-Kuloi craton. It forms part of the extensive Devonian magmatic event of the northern Baltic Shield and Kola Peninsula. Two main groups of kimberlites can be distinguished within the province: (1) kimberlites from the diamondiferous Zolotitsa field that have geochemical and isotopic affinities with Group 2 kimberlites and lamproites; (2) diamond-poor Ti-Fe-rich kimberlites from other Arkhangelsk fields that have geochemical and isotopic affinities with Group 1 kimberlites. However, the Zolotitsa and Ti-Fe-rich kimberlites have mineralogical characteristics that are not typical for their respective assigned kimberlite group classifications. Both groups of Arkhangelsk kimberlites are apparently transitional to Group 1 kimberlites, Group 2 kimberlites and lamproites as they are defined elsewhere in the world. An associated kimberlite from the Mela Sill Complex has strong affinities with carbonatites. The low Al 2O 3, high Ni and Cr contents, and high Mg# in both groups of kimberlites indicate strongly depleted lherzolitic-harzburgitic mantle sources. Trace element patterns show a variable enrichment of incompatible elements and strong LREE enrichment. However, kimberlites from the Zolotitsa field have overall lower trace element abundances and less steep REE patterns, suggesting a higher degree of partial melt and/or a less enriched source compared to that of the Ti-Fe-rich kimberlites. A calciocarbonatite of the Mela Sill Complex has trace element and REE patterns typical of other carbonatites closely associated with kimberlites. 87Sr/ 86Sri and 143Nd/ 144Ndi isotope compositions of the Arkhangelsk kimberlites and carbonatite reveal that at least two mantle sources are required to explain the isotopic variation: (1) most of the Zolotitsa and Mela kimberlites and the Mela carbonatite are derived from an ancient enriched lithospheric source (EMI); (2) the Ti-Fe-rich kimberlites are derived from a plume-related asthenospheric mantle source with an isotopic composition close to Bulk Earth. Present-day Pb isotope compositions reveal that the Zolotitsa kimberlites have values close to Group 1 kimberlites. However, the Ti-Fe-rich kimberlites generally have slightly more radiogenic Pb isotope values.

Investigating the behaviour of Mg isotopes during the formation of clay minerals

NASA Astrophysics Data System (ADS)

Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.

2014-03-01

We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around -2‰, the generation of bulk δ26Mg values of <-0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ˜0.3-0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

Quantifying dispersal rates and distances in North American martens: a test of enriched isotope labeling

Treesearch

Jonathan N. Pauli; Winston P. Smith; Merav Ben-David

2012-01-01

Advances in the application of stable isotopes have allowed the quantitative evaluation of previously cryptic ecological processes. In particular, researchers have utilized the predictable spatial patterning in natural abundance of isotopes to better understand animal dispersal and migration. However, quantifying dispersal via natural abundance alone has proven to be...

Osmium Isotope Compositions of Komatiite Sources Through Time

NASA Astrophysics Data System (ADS)

Walker, R. J.

2001-12-01

Extending Os isotopic measurements to ancient plume sources may help to constrain how and when the well-documented isotopic heterogeneities in modern systems were created. Komatiites and picrites associated with plume-related volcanism are valuable tracers of the Os isotopic composition of plumes because of their typically high Os concentrations and relatively low Re/Os. Re-Os data are now available for a variety of Phanerozoic, Proterozoic and Archean komatiites and picrites. As with modern plumes, the sources of Archean and Proterozoic komatiites exhibit a large range of initial 187Os/188Os ratios. Most komatiites are dominated by sources with chondritic Os isotopic compositions (e.g. Song La; Norseman-Wiluna; Pyke Hill; Alexo), though some (e.g. Gorgona) derive from heterogeneous sources. Of note, however, two ca. 2.7 Ga systems, Kostomuksha (Russia) and Belingwe (Zimbabwe), have initial ratios enriched by 2-3% relative to the contemporary convecting upper mantle. These results suggest that if the 187Os enrichment was due to the incorporation of minor amounts of recycled crust into the mantle source of the rocks, the crust formed very early in Earth history. Thus, the Os results could reflect derivation of melt from hybrid mantle whose composition was modified by the addition of mafic crustal material that would most likely have formed between 4.2 and 4.5 Ga. Alternately, the mantle sources of these komatiites may have derived a portion of their Os from the putative 187Os - and 186Os -enriched outer core. For this hypothesis to be applicable to Archean rocks, an inner core of sufficient mass would have to have crystallized sufficiently early in Earth history to generate an outer core with 187Os enriched by at least 3% relative to the chondritic average. Using the Pt-Re-Os partition coefficients espoused by our earlier work, and assuming linear growth of the inner core started at 4.5 Ga and continued to present, would yield an outer core at 2.7 Ga with a gamma Os value of only +1.2 and a 186Os/188Os enrichment relative to the contemporary upper mantle of only +13 ppm. Greater isotopic enrichments could have been achieved by 2.7 Ga if either the inner core comprised >2.8% of the mass of the core by 2.7 Ga, or if Re and Os solid metal-liquid metal D's for core crystallization were greater that those applied in the initial calculation.

The production of He-3 and heavy ion enrichment in He-3-rich flares by electromagnetic hydrogen cyclotron waves

NASA Technical Reports Server (NTRS)

Temerin, M.; Roth, I.

1992-01-01

A new model is presented for the production of He-3 and heavy ion enrichments in He-3-rich flares using a direct single-stage mechanism. In analogy with the production of electromagnetic hydrogen cyclotron waves in earth's aurora by electron beams, it is suggested that such waves should exist in the electron acceleration region of impulsive solar flares. Both analytic and test-particle models of the effect of such waves in a nonuniform magnetic field show that these waves can selectively accelerate He-3 and heavy ions to MeV energies in a single-stage process, in contrast to other models which require a two-stage mechanism.

Barium isotope fractionation during experimental formation of the double carbonate BaMn[CO3](2) at ambient temperature.

PubMed

Böttcher, Michael E; Geprägs, Patrizia; Neubert, Nadja; von Allmen, Katja; Pretet, Chloé; Samankassou, Elias; Nägler, Thomas F

2012-09-01

In this study, we present the first experimental results for stable barium (Ba) isotope ((137)Ba/(134)Ba) fractionation during low-temperature formation of the anhydrous double carbonate BaMn[CO(3)](2). This investigation is part of an ongoing work on Ba fractionation in the natural barium cycle. Precipitation at a temperature of 21±1°C leads to an enrichment of the lighter Ba isotope described by an enrichment factor of-0.11±0.06‰ in the double carbonate than in an aqueous barium-manganese(II) chloride/sodium bicarbonate solution, which is within the range of previous reports for synthetic pure BaCO (3) (witherite) formation.

U, Th, and Pb isotopes in hot springs on the Juan de Fuca Ridge

NASA Technical Reports Server (NTRS)

Chen, J. H.

1987-01-01

Concentrations and isotopic compositions of U, Th, and Pb in three hydrothermal fluids from the Juan de Fuca Ridge were determined from samples obtained by the Alvin submersible. The samples were enriched in Pb and Th relative to deep-sea water, and were deficient in U. No clear relationship with Mg was found, suggesting nonideal mixing between the hot hydrothermal fluids and the cold ambient seawater. Values for U-234/U-238 have a seawater signature, and show a U-234 enrichment relative to the equilibrium value. The Pb isotopic composition has a uniform midocean ridge basalt signature, and it is suggested that Pb in these fluids may represent the best average value of the local oceanic crust.

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

PubMed

Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

Prediction of equilibrium distributions of isotopologues for methane, ethane and propane using density functional theory

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Peterson, Brian; Eiler, John

2016-10-01

Many previous studies have examined abundances of deuterium (D) and 13C within small organic molecules. Recent advances in analytical instrumentation add the abilities to measure site-specific and multiply substituted isotopologues of natural organics. Here we perform first-principles calculations of the equilibrium distributions of 13C and D in the volatile alkanes (including both single and multiple substitutions), as a guide to the interpretation of current measurements and as a basis for anticipating isotope effects that might be examined with future analytical techniques. The models we present illustrate several common themes of the isotopic structures of the small alkanes, including; temperature dependent enrichment of clumped isotope species, with amplitudes in the order D-D > 13C-D > 13C-13C; similarity in strength of such clumped isotope effects between different molecules (e.g., 13C-D clumping is ∼5‰ enriched at 300 K in methane, ethane and propane); a ∼10× contrast between the amplitudes of stronger adjacent substitution of two heavy isotopes vs. weaker non-adjacent substitution; temperature-dependent site-specific fractionation of D and 13C into interior positions of molecules relative to terminal methyl groups; and a relatively simple additive effect to the overall amplitude of enrichment when clumped and site specific effects combine in the same isotopologue. We suggest that the most promising tools suggested by our results are isotopic thermometers based on site-specific distribution of deuterium, which exhibits strong (∼100‰), highly temperature dependent fractionation between methyl groups and methylene carbon positions in propane (and likely other larger n-alkanes).

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

NASA Astrophysics Data System (ADS)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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

PubMed

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

2015-04-10

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep. Copyright © 2015, American Association for the Advancement of Science.

Hybrid isotope separation scheme

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus. 2 figures.

Recycle of enriched Mo targets for economic production of 99Mo/ 99mTc medical isotope without use of enriched uranium

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

Tkac, Peter; Vandegrift, George F.

2015-08-09

A new recycle process for recovery of enriched 98Mo or 100Mo used for production of 99Mo/ 99mTc medical isotope was developed. In this process, Mo is precipitated from spent NorthStar Mo/Tc generator solution containing ~200 g/L Mo as K 2MoO 4 in 5 M KOH using acetic acid and then washed with nitric acid. High purification factors from potassium were achieved, and typical Mo recovery yields were ~95 %. In conclusion, the recycle process was performed with up to 260 g of Mo per batch and can be easily implemented for processing of up to 400 g of Mo.

The formation of chondrules at high gas pressures in the solar nebula.

PubMed

Galy, A; Young, E D; Ash, R D; O'Nions, R K

2000-12-01

High-precision magnesium isotope measurements of whole chondrules from the Allende carbonaceous chondrite meteorite show that some aluminum-rich Allende chondrules formed at or near the time of formation of calcium-aluminum-rich inclusions and that some others formed later and incorporated precursors previously enriched in magnesium-26. Chondrule magnesium-25/magnesium-24 correlates with [magnesium]/[aluminum] and size, the aluminum-rich, smaller chondrules being the most enriched in the heavy isotopes of magnesium. These relations imply that high gas pressures prevailed during chondrule formation in the solar nebula.

Human variation: delta/sup 13/C in adult bone collagen and the relation to diet in an isochronous C/sub 4/ (maize) archaeological population

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

Bumsted, M.P.

1984-10-01

Analysis of the stable isotopes of carbon (/sup 13/C and /sup 12/C in the standard ratio delta/sup 13/C) can distinguish the relative contributions of meat, cereals, and other plant foods to the diets of prehistoric people. This dissertation has examined an isochronous (non-cemetery) population of prehistoric Americans to ascertain the natural variation in isotopic composition amongst a group of maize-eaters. The seventeen adult females and fifteen adult males represent the largest human data set of prehistoric or contemporary samples for study of natural isotopic enrichment in which genetic, economic, disease, and temporal variables were controlled. Procedures for purifying remnant bonemore » protein from archaeological samples were developed or modified specifically to determine isotopic measurement. Cryogenic milling, cold acid demineralizing, gelatinizing, and an XAD-2 resin column were used to remove soil contaminants while preserving the chemical integrity of the bone protein. Measurements of total elemental carbon, hydrogen, and nitrogen of the unprocessed bone; amino acid analysis of selected gelatin samples; and stable carbon isotopic analysis were used to assess sample quality. Isotope values were lognormally distributed in this population (anti X = -1.15%) with the distribution and the means amongst males (anti X = -1.18%) significantly different from that of females (anti X = -1.13%). The isotopic diet model can be graphed with equilateral triangular coordinates to represent the relative contributions of meat, maize, and other plant foods. The graph can predict the maximum food contributions to the delta/sup 13/C of the prehistoric individuals measured. Isotopic variation in human bone protein is only partly due to the variable amount of enriched foods in the diet. Tissue enrichment which occurs at various metabolic levels must also be considered. 316 references, 20 figures, 10 tables.« less

Nitrous oxide nitrification and denitrification 15N enrichment factors from Amazon forest soils.

PubMed

Pérez, Tibisay; Garcia-Montiel, Diana; Trumbore, Susan; Tyler, Stanley; de Camargo, Plínio; Moreira, Marcelo; Piccolo, Marisa; Cerri, Carlos

2006-12-01

The isotopic signatures of 15N and 18O in N2O emitted from tropical soils vary both spatially and temporally, leading to large uncertainty in the overall tropical source signature and thereby limiting the utility of isotopes in constraining the global N2O budget. Determining the reasons for spatial and temporal variations in isotope signatures requires that we know the isotope enrichment factors for nitrification and denitrification, the two processes that produce N2O in soils. We have devised a method for measuring these enrichment factors using soil incubation experiments and report results from this method for three rain forest soils collected in the Brazilian Amazon: soil with differing sand and clay content from the Tapajos National Forest (TNF) near Santarém, Pará, and Nova Vida Farm, Rondônia. The 15N enrichment factors for nitrification and denitrification differ with soil texture and site: -111 per thousand +/- 12 per thousand and -31 per thousand +/- 11 per thousand for a clay-rich Oxisol (TNF), -102 per thousand +/- 5 per thousand and -45 per thousand +/- 5 per thousand for a sandier Ultisol (TNF), and -10.4 per thousand +/- 3.5 per thousand (enrichment factor for denitrification) for another Ultisol (Nova Vida) soil, respectively. We also show that the isotopomer site preference (delta15Nalpha - delta15Nbeta, where alpha indicates the central nitrogen atom and beta the terminal nitrogen atom in N2O) may allow differentiation between processes of production and consumption of N2O and can potentially be used to determine the contributions of nitrification and denitrification. The site preferences for nitrification and denitrification from the TNF-Ultisol incubated soils are: 4.2 per thousand +/- 8.4 per thousand and 31.6 per thousand +/- 8.1 per thousand, respectively. Thus, nitrifying and denitrifying bacteria populations under the conditions of our study exhibit significantly different 15N site preference fingerprints. Our data set strongly suggests that N2O isotopomers can be used in concert with traditional N2O stable isotope measurements as constraints to differentiate microbial N2O processes in soil and will contribute to interpretations of the isotopic site preference N2O values found in the free troposphere.

Characterization of the N2O isotopic composition (15N, 18O and N2O isotopomers) emitted from incubated Amazon forest soils. Implications for the global N2O isotope budget

NASA Astrophysics Data System (ADS)

Pérez, T.; García, D.; Trumbore, S.; Tyler, S.; de Camargo, P.; Moreira, M.; Piccolo, M.; Park, S.; Boering, K.; Cerri, C.

2003-04-01

Tropical rain forest soils are the largest natural source of N2O to the atmosphere. Uncertainty in the signature of this source limits the utility of isotopes in constraining the global N2O budget. Differentiating the relative contribution of nitrification and denitrification to the emitted N2O using stable isotopes has been difficult due to the lack of enrichment factors values for each process measured in situ. We have devised a method for measuring enrichment factors using soil incubation experiments. We selected three Amazon rain forest soils: (1) Clay and (2) Sandy from Santarem, Pará State, and (3) Sandy from Nova Vida Farm, Rondonia State, Brazil. The enrichment factor values for nitrification and denitrification are: -97.8±4.2 and -9.9±3.8 per mil for clay Santarem soil, -86.8±4.3 and -45.2±4.5 per mil for sandy Santarem soil and-112.6±3.8 and -10.4±3.5 per mil for Nova Vida Farm soils, respectively. Our results show that enrichment factors for both processes differ with soil texture and location. The enrichment factors for nitrification are significantly smaller than the range reported in the literature (-66 to -42 per mil). Also, the enrichment factors for the Santarem soils (clay and sandy) differ significantly implying that soil texture (which will affect the soil air filled pore space at a given water content) is influencing the bacteria isotopic discrimination. However, the enrichment factors for the Santarem clay sand Nova Vida sandy soils do not differ by much. This suggests that the enrichment factors not only can be affected by texture but also by the microbial fauna present in these soils. We also determined the measurement of the N2O positional dependence. N2O is a linear molecule with two nitrogen atoms. The 15N isotope can be located in either the central nitrogen (alpha position) or in the terminal nitrogen (beta position). The isotopomer site preference (15N alpha - 15N beta) can be used to differentiate processes of production and consumption of N2O as a potential method to determine the contributions of nitrification and denitrification. We measured the isotopomer composition of the incubated soils and calculated the site preference of each process for each soils. The site preference for nitrification and denitrification are: -114.5 and 56.6 per mil for clay Santarem soil, -75.2 and 11.8 per mil for sandy Santarem soil and -209.7 and 28.8 per mil for Nova Vida Farm soils, respectively. To our knowledge these are the first N2O isotopomer characterizations for nitrification and denitrification in soils. The results show that nitrifying bacteria population has 15N site preference fingerprints smaller by up to 200 per mil than denitrifying bacteria. This data set strongly suggests that N2O isotopomers can be used in concert with traditional N2O stable isotope measurements as constraints to differentiate microbial processes producing N2O. We can conclude that nitrifiers produce N2O with a smaller site preference values and more negative del 15N beta than do denitrifiers. These results show a new proxy to differentiate N2O formation processes in soil and will contribute to produce interpretations of the site preference isotopomeric N2O values found in the troposphere.

10 CFR 51.20 - Criteria for and identification of licensing and regulatory actions requiring environmental...

Code of Federal Regulations, 2010 CFR

2010-01-01

... design capacity license to operate an isotopic enrichment plant pursuant to part 50 of this chapter. (4... uranium enrichment facility. (11) Issuance of renewal of a license authorizing receipt and disposal of...

Silicon Isotope Geochemistry of Ocean Island Basalts: Search for Deep Mantle Heterogeneities and Evidence for Recycled Altered Oceanic Crust

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2014-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but debate about the degree and cause of variability persists. The study of silicon (Si) isotopes in OIBs has the potential to elucidate mantle heterogeneities. Relatively large (~several per mil) Si isotopic fractionation occurs in low-temperature environments during precipitation from dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1], but only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed due to high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material in OIB source regions in a manner similar to more conventional stable isotope systems, such as oxygen. Here we present the first comprehensive suite of high-precision Si isotopic data obtained by MC-ICP-MS for a diverse set of OIBs representing the EM-1, EM-2, and HIMU mantle components. In general, the Si isotopic compositions of OIBs analyzed here are agreement with previous estimates for Bulk Silicate Earth (BSE). However, small systematic variations are present; the HIMU end-member Mangaia and HIMU-type Cape Verde island São Nicolau are enriched in the light isotopes of Si (δ30Si = -0.37 ± 0.06‰ and δ30Si = -0.39 ± 0.04‰, respectively; errors are 2sd), with compositions intermediary between Mid Ocean Ridge Basalts and chondritic values. Additionally, Iceland samples from volcanic complexes in the Northern Rift Zone show similar Si isotope compositions (on average, δ30Si = -0.40 ± 0.06‰). In contrast, the δ30Si averages of the EM-1 end-member Pitcairn (-0.28 ± 0.07‰), the EM-2 end-member Samoa (-0.31 ± 0.07‰) and other OIB localities do not show any significant difference from previous estimates for the δ30Si value of BSE [3]. The Si isotopic variability in some HIMU-type and Icelandic OIBs most likely reflects the incorporation of recycled altered oceanic crust in the plume source. However, the sampling of a primitive reservoir enriched in the light isotopes of Si, as suggested by [4], cannot be ruled out as a potential source of Si isotope variations in OIBs. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Huang et al., GCA 2014

Hf-Nd isotope constraints on the origin of the Cretaceous Caribbean plateau and its relationship to the Galápagos plume

NASA Astrophysics Data System (ADS)

Thompson, P. M. E.; Kempton, P. D.; White, R. V.; Kerr, A. C.; Tarney, J.; Saunders, A. D.; Fitton, J. G.; McBirney, A.

2004-01-01

Formation of the Cretaceous Caribbean plateau, including the komatiites of Gorgona, has been linked to the currently active Galápagos hotspot. We use Hf-Nd isotopes and trace element data to characterise both the Caribbean plateau and the Galápagos hotspot, and to investigate the relationship between them. Four geochemical components are identified in the Galápagos mantle plume: two 'enriched' components with ɛHf and ɛNd similar to enriched components observed in other mantle plumes, one moderately enriched component with high Nb/Y, and a fourth component which most likely represents depleted MORB source mantle. The Caribbean plateau basalt data form a linear array in Hf-Nd isotope space, consistent with mixing between two mantle components. Combined Hf-Nd-Pb-Sr-He isotope and trace element data from this study and the literature suggest that the more enriched Caribbean end member corresponds to one or both of the enriched components identified on Galápagos. Likewise, the depleted end member of the array is geochemically indistinguishable from MORB and corresponds to the depleted component of the Galápagos system. Enriched basalts from Gorgona partially overlap with the Caribbean plateau array in ɛHf vs. ɛNd, whereas depleted basalts, picrites and komatiites from Gorgona have a high ɛHf for a given ɛNd, defining a high- ɛHf depleted end member that is not observed elsewhere within the Caribbean plateau sequences. This component is similar, however, in terms of Hf-Nd-Pb-He isotopes and trace elements to the depleted plume component recognised in basalts from Iceland and along the Reykjanes Ridge. We suggest that the Caribbean plateau represents the initial outpourings of the ancestral Galápagos plume. Absence of a moderately enriched, high Nb/Y component in the older Caribbean plateau (but found today on the island of Floreana) is either due to changing source compositions of the plume over its 90 Ma history, or is an artifact of limited sampling. The high- ɛHf depleted component sampled by the Gorgona komatiites and depleted basalts is unique to Gorgona and is not found in the Caribbean plateau. This may be an indication of the scale of heterogeneity of the Caribbean plateau system; alternatively Gorgona may represent a separate oceanic plateau derived from a completely different Pacific plume, such as the Sala y Gomez.

Trace Element and Cu Isotopic Tracers of Subsurface Flow and Transport in Wastewater Irrigated Soils

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

An understanding of subsurface flow paths is critical for quantifying the fate of contaminants in wastewater irrigation systems. This study investigates the subsurface flow of wastewater by quantifying the distribution of trace contaminants in wastewater irrigated soils. Soil samples were collected from the upper 1m of two wetlands at Penn State University's wastewater irrigation site, at which all effluent from the University's wastewater treatment plant has been sprayed since 1983. Major and trace element and Cu isotopic composition were determined for these samples, in addition to wastewater effluent and bedrock samples. The upper 20 cm of each wetland shows an enrichment of Bi, Cd, Cr, Cu, Mo, Ni, Pb, and Zn concentrations relative to deep (>1m) soils at the site by a factor of 1.7-3.5. Each wetland also has a subsurface clay rich horizon with Bi, Cu, Li, Ni, Pb, and Zn concentrations enriched by a factor of 1.4 to 5 relative to deep soils. These subsurface horizons directly underlie intervals that could facilitate preferential effluent flow: a gravel layer in one wetland, and a silty loam with visible mottling, an indication of dynamic water saturation, in the other. Trace metal concentrations in other horizons from both wetlands fall in the range of the deep soils. Significant variability in Cu isotopic composition is present in soils from both wetlands, with δ65Cu values ranging from 0.74‰ to 5.09‰. Soil δ65Cu correlates well with Cu concentrations, with lighter δ65Cu associated with higher concentrations. The Cu isotopic composition of the zones of metal enrichment are comparable to the ostensible average wastewater effluent δ65Cu value (0.61‰), while other horizons have considerably heavier δ65Cu values. We hypothesize that wastewater is the source of the metal enrichments, as each of the enriched elements are present as contaminants in wastewater, and the enrichments are located in clay-rich horizons conducive to trace metal immobilization due to adsorption. This hypothesis will be further tested by modeling with the reactive transport code CrunchTope. This study provides evidence that trace element and isotopic composition of soils can be useful tracers of subsurface hydrologic pathways and elemental fate and transport.

Preliminary study on copper isotopes of the Zijinshan ore field, Fujian Province, SE China

NASA Astrophysics Data System (ADS)

Zhao, Hai-Xiang

2017-04-01

Zijinshan Cu-Au polymetallic ore field is located in Southeast China, tectonically belonging to the Interior Cathaysia Block. It is a complete porphyry-epithermal mineralization system, including Luoboling porphyry Cu-Mo deposit, Zijinshan high sulfidation Cu-Au deposit, Yueyang low sulfidation Ag-Au deposit, Wuziqilong and Longjiangting transitional style Cu deposits, etc. Main ore minerals from Zijinshan and Wuziqilong deposits are covellite and digenite. Copper isotopic compositions of these two minerals were analyzed. Copper isotope ratios are reported in the standard delta notation: δ65 Cu‰¯[ (65Cu/63Cu)Sample/(65Cu/63Cu) ERM-AE633-1] ×1000. The overall δ65Cu values for the analysed samples vary from -2.76 to 1.33‰Ṫhe Zijinshan Cu-Au deposit show large Cu isotopic variability (-2.76 to 1.33), among which covellite samples range from -2.76‰ to 0.38‰ with -0.79‰ in average and digenite samples range from -1.8‰ to 1.33‰ with -0.11‰ in average. During the leaching process of hypogene sulphides, 65Cu was leached more easily and then trapped in the supergene enrichment zone. Therefore, enrichment minerals should be enriched in 65Cu and the leached cap enriched in 63Cu. Thus the relationship of δ65Cu values for different Cu reservoirs should be leached cap minerals < hypogene sulphides < enrichment minerals. Nonexistence of enriched δ65Cu values indicate that the major copper minerals (mainly covellite and digenite) in the Zijinshan Cu-Au deposit and Wuziqilong Cu deposit are of hypogene origin rather than secondary origin. At the Wuziqilong Cu deposit, Cu isotopes has narrow range from 0.16‰ to 0.43‰ with 0.31‰ in average, which is typically of hypogene origin. Two coexisting covellite -digenite fractionations (δ65Cu =δ65Cucovellite - δ65Cudigenite) are 0.27‰ and 0.18‰ relatively. For minerals of the Cu-S system, from chalcocite (Cu2S) to covellite (CuS), proportions of Cu(II) become higher and higher. The classical definition of the crystallographic structure of covellite indicated that one third of the Cu is Cu(II) and digenite (Cu1.8S) has one ninth of Cu(II). Therefore, covellite is more oxidized species and has higher δ65Cu compared with coexisting digenite.

Hybrid Interferometric/Dispersive Atomic Spectroscopy For Nuclear Materials Analysis

NASA Astrophysics Data System (ADS)

Morgan, Phyllis K.

Laser-induced breakdown spectroscopy (LIBS) is an optical emission spectroscopy technique that holds promise for detection and rapid analysis of elements relevant for nuclear safeguards and nonproliferation, including the measurement of isotope ratios. One important application of LIBS is the measurement of uranium enrichment (235U/238U), which requires high spectral resolution (e.g., 25 pm for the 424.437 nm U II line). Measuring uranium enrichment is important in nuclear nonproliferation and safeguards because the uranium highly enriched in the 235U isotope can be used to construct nuclear weapons. High-resolution dispersive spectrometers necessary for such measurements are typically bulky and expensive. A hybrid interferometric/dispersive spectrometer prototype, which consists of an inexpensive, compact Fabry-Perot etalon integrated with a low to moderate resolution Czerny-Turner spectrometer, was assembled for making high-resolution measurements of nuclear materials in a laboratory setting. To more fully take advantage of this low-cost, compact hybrid spectrometer, a mathematical reconstruction technique was developed to accurately reconstruct relative line strengths from complex spectral patterns with high resolution. Measurement of the mercury 313.1555/313.1844 nm doublet from a mercury-argon lamp yielded a spectral line intensity ratio of 0.682, which agrees well with an independent measurement by an echelle spectrometer and previously reported values. The hybrid instrument was used in LIBS measurements and achieved the resolution needed for isotopic selectivity of LIBS of uranium in ambient air. The samples used were a natural uranium foil (0.7% of 235U) and a uranium foil highly enriched in 235U to 93%. Both samples were provided by the Penn State University's Breazeale Nuclear Reactor. The enrichment of the uranium foils was verified using a high-purity germanium detector and dedicated software for multi-group spectral analysis. Uranium spectral line widths of ˜10 pm were measured at a center wavelength 424.437 nm, clearly discriminating the natural from the highly enriched uranium at that wavelength. The 424.167 nm isotope shift (˜6 pm), limited by spectral broadening, was only partially resolved but still discernible. This instrument and reconstruction method could enable the design of significantly smaller, portable high-resolution instruments with isotopic specificity, benefiting nuclear safeguards, treaty verification, nuclear forensics, and a variety of other spectroscopic applications.

Estimating pothole wetland connectivity to Pipestem Creek ...

EPA Pesticide Factsheets

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding how reliant stream flow is on wetlands within their watershed. We used the isotopic evaporation signal in water to examine wetland-stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie-pothole wetlands. During a wetter-than-normal decade, Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched pothole wetlands. If evaporation was mainly occurring within the stream, we expected the evaporation signal to increase from upstream towards downstream. However, the signal either remained similar or decreased downstream over the two years of sampling. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment. Using isotopic theory and discharge data, we estimated the surface area of open water necessary to generate the evaporation signal found within Pipestem Creek over time. The range of evaporating surface-area estimates was highly dynamic, spanning from 35 to 2380 ha of open water contributing to streamflow over time, and varied primarily with the amount of discharge. The median value (417 ha) was well above the surface area of the Pipestem Creek network (245 ha), and only two periods

Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s.

PubMed

Miller, Laurence G; Baesman, Shaun M; Oremland, Ronald S

2015-11-01

We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Acetylene-Fermentation-Isotope fractionation-Enceladus-Life detection.

Nuclear reactions in shock wave front during supernova events

NASA Technical Reports Server (NTRS)

Lavrukhina, A. K.

1985-01-01

The new unique isotopic anomalous coponent of Xe(XeX) was found in the carbonaceous chondrites. It is enriched in light shielded isotopes (124Xe and 126Xe) and in heavy nonshielded isotopes (134Xe and 136Xe. All characteristics of Xe-X can be explained by a model of nucleosynthesis of the Xe isotopes in shock wave front passed through the He envelope during supernova events. The light isotopes are created by p process and the heavy isotopes are created by n process (slow r process). They were captured with high temperature carbon grains condensing by supernova shock waves.

Revisiting streamside trees that do not use stream water: can the two water worlds hypothesis and snowpack isotopic effects explain a missing water source?: Riparian tree water sources

DOE PAGES

Bowling, David R.; Schulze, Emily S.; Hall, Steven J.

2016-10-14

We revisit a classic ecohydrological study that showed streamside riparian trees in a semiarid mountain catchment did not use perennial stream water. The original study suggested that mature individuals of Acer negundo, Acer grandidentatum, and other species were dependent on water from “deeper strata,” possibly groundwater. We used a dual stable isotope approach (δ 18O and δ 2H) to further examine the water sources of these trees. We tested the hypothesis that groundwater was the main tree water source, but found that neither groundwater nor stream water matched the isotope composition of xylem water during two growing seasons. Soil watermore » (0–1 m depth) was closest to and periodically overlapped with xylem water isotope composition, but overall, xylem water was isotopically enriched compared to all measured water sources. The “two water worlds” hypothesis postulates that soil water comprises isotopically distinct mobile and less mobile pools that do not mix, potentially explaining this disparity. We further hypothesized that isotopic effects during snowpack metamorphosis impart a distinct isotope signature to the less mobile soil water that supplies summer transpiration. Depth trends in water isotopes following snowmelt were consistent with the two water worlds hypothesis, but snow metamorphic isotope effects could not explain the highly enriched xylem water. Thus, the dual isotope approach did not unambiguously determine the water source(s) of these riparian trees. Further exploration of physical, geochemical, and biological mechanisms of water isotope fractionation and partitioning is necessary to resolve these data, highlighting critical challenges in the isotopic determination of plant water sources.« less

Revisiting streamside trees that do not use stream water: can the two water worlds hypothesis and snowpack isotopic effects explain a missing water source?: Riparian tree water sources

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

Bowling, David R.; Schulze, Emily S.; Hall, Steven J.

We revisit a classic ecohydrological study that showed streamside riparian trees in a semiarid mountain catchment did not use perennial stream water. The original study suggested that mature individuals of Acer negundo, Acer grandidentatum, and other species were dependent on water from “deeper strata,” possibly groundwater. We used a dual stable isotope approach (δ 18O and δ 2H) to further examine the water sources of these trees. We tested the hypothesis that groundwater was the main tree water source, but found that neither groundwater nor stream water matched the isotope composition of xylem water during two growing seasons. Soil watermore » (0–1 m depth) was closest to and periodically overlapped with xylem water isotope composition, but overall, xylem water was isotopically enriched compared to all measured water sources. The “two water worlds” hypothesis postulates that soil water comprises isotopically distinct mobile and less mobile pools that do not mix, potentially explaining this disparity. We further hypothesized that isotopic effects during snowpack metamorphosis impart a distinct isotope signature to the less mobile soil water that supplies summer transpiration. Depth trends in water isotopes following snowmelt were consistent with the two water worlds hypothesis, but snow metamorphic isotope effects could not explain the highly enriched xylem water. Thus, the dual isotope approach did not unambiguously determine the water source(s) of these riparian trees. Further exploration of physical, geochemical, and biological mechanisms of water isotope fractionation and partitioning is necessary to resolve these data, highlighting critical challenges in the isotopic determination of plant water sources.« less

Isotope pattern deconvolution as rising tool for isotope tracer studies in environmental research

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Zitek, Andreas; Prohaska, Thomas

2014-05-01

During the last decade stable isotope tracers have emerged as versatile tool in ecological research. Besides 'intrinsic' isotope tracers caused by the natural variation of isotopes, the intentional introduction of 'extrinsic' enriched stable isotope tracers into biological systems has gained significant interest. Hereby the induced change in the natural isotopic composition of an element allows amongst others for studying the fate and fluxes of metals, trace elements and species in organisms or provides an intrinsic marker or tag of particular biological samples. Due to the shoreless potential of this methodology, the number of publications dealing with applications of isotope (double) spikes as tracers to address research questions in 'real world systems' is constantly increasing. However, some isotope systems like the natural Sr isotopic system, although potentially very powerful for this type of application, are still rarely used, mainly because their adequate measurement/determination poses major analytical challenges; as e.g. Sr is available in significant amounts in natural samples. In addition, biological systems underlie complex processes such as metabolism, adsorption/desorption or oxidation/reduction. As a consequence, classic evaluation approaches such as the isotope dilution mass spectrometry equation are often not applicable because of the unknown amount of tracer finally present in the sample. Isotope pattern deconvolution (IPD), based on multiple linear regression, serves as simplified alternative data processing strategy to double spike isotope dilution calculations. The outstanding advantage of this mathematical tool lies in the possibility of deconvolving the isotope pattern in a spiked sample without knowing the quantities of enriched isotope tracer being incorporated into the natural sample matrix as well as the degree of impurities and species-interconversion (e.g. from sample preparation). Here, the potential of IPD for environmental tracer studies is critically discussed, where special emphasis is set on evaluating different data processing strategies on the example of enriched stable Sr isotopes.1 The analytical key parameters such as blank (Kr, Sr and Rb), variation of the natural Sr isotopic composition in the sample, mass bias, interferences (Rb) and total combined uncertainty are considered. A full metrological protocol for data processing using IPD is presented based on data gained during two transgenerational marking studies of fish, where the transfer of a Sr isotope double spike (84Sr and 86Sr) from female spawners of common carp (Cyprinus carpio L.) and brown trout (Salmo trutta f.f.)2 to the centre of the otoliths of their offspring was studied by (LA)-MC-ICP-MS. 1J. Irrgeher, A. Zitek, M. Cervicek and T. Prohaska, J. Anal. At. Spectrom., 2014, 29, 193-200. 2A. Zitek, J. Irrgeher, M. Kletzl, T. Weismann and T. Prohaska, Fish. Manage. Ecol., 2013, 20, 654-361.

Compound-Specific Carbon and Hydrogen Isotope Analysis - Field Evidence of MTBE Bioremediation

NASA Astrophysics Data System (ADS)

Kuder, T.; Kolhatkar, R. V.; Philp, P.; Wilson, J. T.; Landmeyer, J. E.; Allen, J.

2002-12-01

Compound-specific stable isotope analysis allows opportunity to determine the isotopic ratios of individual contaminants. The technique has been applied to confirm biodegradation in studies of chlorinated solvents and recently BTEX, MTBE and TBA. Chemical reactions (including bio- and inorganic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting with enrichment of the unreacted substrate in the heavier isotopic species (13C, D), referred to as kinetic isotopic fractionation, so that the extent of fractionation may be used as a proxy for biodegradation. Processes such as volatilization, sorption etc., result in minimal degree of fractionation and do not interfere with the isotopic signal due to biodegradation. The results presented here show the first successful applications of compound-specific isotope analysis to understanding MTBE biodegradation in the field, at both aerobic and anaerobic sites. Observed fractionations suggest that two different biodegradation pathways may be involved. At a number of anaerobic locations major fractionation effects were observed for both C and H; enrichment factors Ÿnfor both elements were approaching or exceeding -10. A laboratory microcosm study using an enrichment culture yielded similar results (C data only). A characteristic feature of these sites was the presence of high concentrations of TBA. Conversely, at a number of sites, the C composition remained stable with little fractionation and stayed within the analytical precision range or changed minimally, while H displayed significant fractionation in excess of 60 per mil. Moderate agreement of the data with Rayleigh fractionation model was observed, suggesting that biodegradation effect was distorted by variability at the source or the plume was not homogeneous. The enrichment factor calculated for these data is similar to the one Ÿnpublished for aerobic microcosm of MTBE-degrading culture from Vandenberg AFB by Gray et al. (Env. Sci. Tech., 2002, 36, 1931-1938) and appears to be in excess of -60 for H and under -2 for C. The high H fractionation observed under aerobic conditions may be attributed to the initial, monooxygenase transformation of MTBE (cf., Deeb et al., Biodegradation, 2000, 11, 171-186). The anaerobic enzymatic reactions were not characterized yet, but a hydrolytic process may be responsible. Interestingly, isotopic fractionation at an anaerobic site, which was treated by oxygen injection, did not show differences between aerobic and anaerobic parts of the plume. Despite oxygen addition, there was no evidence for monooxygenase activity.

Total synthesis of isotopically enriched Si-29 silica NPs as potential spikes for isotope dilution quantification of natural silica NPs.

PubMed

Pálmai, Marcell; Szalay, Roland; Bartczak, Dorota; Varga, Zoltán; Nagy, Lívia Naszályi; Gollwitzer, Christian; Krumrey, Michael; Goenaga-Infante, Heidi

2015-05-01

A new method was developed for the preparation of highly monodisperse isotopically enriched Si-29 silica nanoparticles ((29)Si-silica NPs) with the purpose of using them as spikes for isotope dilution mass spectrometry (IDMS) quantification of silica NPs with natural isotopic distribution. Si-29 tetraethyl orthosilicate ((29)Si-TEOS), the silica precursor was prepared in two steps starting from elementary silicon-29 pellets. In the first step Si-29 silicon tetrachloride ((29)SiCl4) was prepared by heating elementary silicon-29 in chlorine gas stream. By using a multistep cooling system and the dilution of the volatile and moisture-sensitive (29)SiCl4 in carbon tetrachloride as inert medium we managed to reduce product loss caused by evaporation. (29)Si-TEOS was obtained by treating (29)SiCl4 with absolute ethanol. Structural characterisation of (29)Si-TEOS was performed by using (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform infrared (FTIR) spectroscopy. For the NP preparation, a basic amino acid catalysis route was used and the resulting NPs were analysed using transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential measurements. Finally, the feasibility of using enriched NPs for on-line field-flow fractionation coupled with multi-angle light scattering and inductively coupled plasma mass spectrometry (FFF/MALS/ICP-MS) has been demonstrated. Copyright © 2015 Elsevier Inc. All rights reserved.

Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

NASA Astrophysics Data System (ADS)

Kang, J.; Buyanjargal, A.; Jeen, S. W.

2017-12-01

Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

Investigation into the Feasibility of Highly Enriched Uranium Detection by External Neutron Stimulation (Expanded Study)

DTIC Science & Technology

2006-05-01

26 1.10.1 Radiation Isotope Detector Operation ...... 27 1.10.2 HEU Counts in Radioisotope with 1 kg HEU.. 27 1.10.3 Radiation Isotope ...REACTOR GRADE PLUTONIUM ........... 173 10.2 GAMMA EMITTING ISOTOPES IN CARGO MATERIAL ............. 177 10.3 MCNP ANALYSIS OF GAMMA TRANSPORT FROM A...experiment at USNA using a germanium detector .......................... 31 1-13 Counts in the radiation isotope detector versus counting time for 1

Sr isotopic composition of Afar volcanics and its implication for mantle evolution

NASA Astrophysics Data System (ADS)

Barberi, F.; Civetta, L.; Varet, J.

1980-10-01

Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

LU-HF Age of Martian Meteorite Larkman Nunatek 06319

NASA Technical Reports Server (NTRS)

Shafer, J. T.; Brandon, A. D.; Lapen, T. J.; Righter, M.; Beard, B.; Peslier, A. H.

2009-01-01

Lu-Hf isotopic data were collected on mineral separates and bulk rock powders of LAR 06319, yielding an age of 197+/- 29 Ma. Sm-Nd isotopic data and in-situ LA-ICP-MS data from a thin section of LAR 06319 are currently being collected and will be presented at the 2009 LPSC. These new data for LAR 06319 extend the existing data set for the enriched shergottite group. Martian meteorites represent the only opportunity for ground truth investigation of the geochemistry of Mars [1]. At present, approximately 80 meteorites have been classified as Martian based on young ages and distinctive isotopic signatures [2]. LAR 06319 is a newly discovered (as part of the 2006 ANSMET field season) martian meteorite that represents an important opportunity to further our understanding of the geochemical and petrological constraints on the origin of Martian magmas. Martian meteorites are traditionally categorized into the shergottite, nakhlite, and chassignite groups. The shergottites are further classified into three distinct isotopic groups designated depleted, intermediate, and enriched [3,4] based on the isotope systematics and compositions of their source(s).

Early inner solar system origin for anomalous sulfur isotopes in differentiated protoplanets.

PubMed

Antonelli, Michael A; Kim, Sang-Tae; Peters, Marc; Labidi, Jabrane; Cartigny, Pierre; Walker, Richard J; Lyons, James R; Hoek, Joost; Farquhar, James

2014-12-16

Achondrite meteorites have anomalous enrichments in (33)S, relative to chondrites, which have been attributed to photochemistry in the solar nebula. However, the putative photochemical reactions remain elusive, and predicted accompanying (33)S depletions have not previously been found, which could indicate an erroneous assumption regarding the origins of the (33)S anomalies, or of the bulk solar system S-isotope composition. Here, we report well-resolved anomalous (33)S depletions in IIIF iron meteorites (<-0.02 per mil), and (33)S enrichments in other magmatic iron meteorite groups. The (33)S depletions support the idea that differentiated planetesimals inherited sulfur that was photochemically derived from gases in the early inner solar system (<∼2 AU), and that bulk inner solar system S-isotope composition was chondritic (consistent with IAB iron meteorites, Earth, Moon, and Mars). The range of mass-independent sulfur isotope compositions may reflect spatial or temporal changes influenced by photochemical processes. A tentative correlation between S isotopes and Hf-W core segregation ages suggests that the two systems may be influenced by common factors, such as nebular location and volatile content.

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

NASA Astrophysics Data System (ADS)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

Chlorine isotope fractionation during supergene enrichment of copper

NASA Astrophysics Data System (ADS)

Reich, M.; Barnes, J.; Barra, F.; Milojevic, C.; Drew, D.

2017-12-01

Supergene enrichment of Cu deposits in the Atacama Desert has played a critical role in making this the prime Cu-producing province of the world. The Cu-hydroxychloride atacamite is a major component of supergene zones in this region whereas in similar deposits elsewhere it is rare. Atacamite requires saline water to form and dissolves rapidly when exposed to fresh, meteoric water. Previous chlorine stable isotope data [1] for atacamite mineralization at the Radomiro Tomic, Chuquicamata and Mina Sur Cu deposits show δ37Cl values that range from -0.1 to +0.2‰, indicating a similar nonmagmatic source for the introduction of chloride. However, distal atacamite mineralization on the periphery of these orebodies show more fractionated and lighter δ37Cl values (-3.2 to -0.1‰). Although little disagreement currently exists about the involvement of saline groundwater during the formation of atacamite [2], no δ37Cl data are currently available for atacamite within a single deposit and/or supergene enrichment profile that allow explaining the aforementioned differences in the observed δ37Cl values. Furthermore, no experimental data for chlorine isotope fractionation between Cu-hydroxychloride minerals and water exist that help evaluate possible mechanisms of fractionation along the groundwater flow path. Here we present a new database that combines detailed mineralogical observations with δ37Cl data of atacamite along a thick ( 100 m) supergene enrichment profile at the Barreal Seco IOCG deposit in the Atacama Desert of northern Chile. Chlorine stable isotope data of atacamite vary between -0.62 and +2.1 ‰ and show a well-defined trend where δ37Cl values progressively decrease (become lighter) with depth. These data, when combined with new experimental determinations of chlorine isotope fractionation between atacamite and water, point to changes triggered by the progressive deepening of groundwater tables during Andean uplift and the extreme desiccation of Atacama. References [1] Arcuri T, Brimhall G (2003) The chloride source for atacamite mineralization at the Radomiro Tomic porphyry copper deposit, Northern Chile. Econ Geol 98:1667-1681 [2] Reich M et al. (2009) Supergene enrichment of copper deposits since the onset of modern hyperaridity in the Atacama Desert, Chile. Miner Deposita 44: 497-504

The micro-scale synthesis of (117)Sn-enriched tributyltin chloride and its characterization by GC-ICP-MS and NMR techniques.

PubMed

Peeters, Kelly; Iskra, Jernej; Zuliani, Tea; Ščančar, Janez; Milačič, Radmila

2014-07-01

Organotin compounds (OTCs) are among the most toxic substances ever introduced to the environment by man. They are common pollutants in marine ecosystems, but are also present in the terrestrial environment, accumulated mainly in sewage sludge and landfill leachates. In investigations of the degradation and methylation processes of OTC in environmental samples, the use of enriched isotopic tracers represents a powerful analytical tool. Sn-enriched OTC are also necessary in application of the isotope dilution mass spectrometry technique for their accurate quantification. Since Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) are not commercially available as single species, "in house" synthesis of individual butyltin-enriched species is necessary. In the present work, the preparation of the most toxic butyltin, namely TBT, was performed via a simple synthetic path, starting with bromination of metallic Sn, followed by butylation with butyl lithium. The tetrabutyltin (TeBT) formed was transformed to tributyltin chloride (TBTCl) using concentrated hydrochloric acid (HCl). The purity of the synthesized TBT was verified by speciation analysis using the techniques of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) and nuclear magnetic resonance (NMR). The results showed that TBT had a purity of more than 97%. The remaining 3% corresponded to DBT. TBT was quantified by reverse isotope dilution GC-ICP-MS. The synthesis yield was around 60%. The advantage of this procedure over those previously reported lies in its possibility to be applied on a micro-scale (starting with 10mg of metallic Sn). This feature is of crucial importance, since enriched metallic Sn is extremely expensive. The procedure is simple and repeatable, and was successfully applied for the preparation of (117)Sn-enriched TBTCl from (117)Sn-enriched metal. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

PubMed

Nonose, Naoko; Suzuki, Toshihiro; Shin, Ki-Cheol; Miura, Tsutomu; Hioki, Akiharu

2017-06-29

A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208 Pb and a solution of enriched 204 Pb ( 208 Pb- 204 Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208 Pb: 204 Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208 Pb: 204 Pb in the 208 Pb- 204 Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206 Pb: 204 Pb, 15.6278 ± 0.0036 for 207 Pb: 204 Pb, 38.0626 ± 0.0089 for 208 Pb: 204 Pb, 2.104406 ± 0.00013 for 208 Pb: 206 Pb, and 0.863888 ± 0.000036 for 207 Pb: 206 Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, or one eighth, for 208 Pb: 206 Pb and 207 Pb: 206 Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, the latter contribution is two or three times larger than the former. When the coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method is applied to the analysis of NIST SRM 981, the measured lead isotope ratios are in good agreement with its certified values. This proves that the developed method is not only consistent with the conventional one by NIST SRM 981 but also enables measurement of the lead isotope ratios with higher precision. Copyright © 2017 Elsevier B.V. All rights reserved.

Anaerobic degradation of vinyl chloride in aquifer microcosms.

PubMed

Smits, Theo H M; Assal, Antoine; Hunkeler, Daniel; Holliger, Christof

2011-01-01

The anaerobic degradation potential at a chloroethene-contaminated site was investigated by operating two anoxic column aquifer microcosms enriched in iron(III). One column was fed with vinyl chloride (VC) only (column A) and one with VC and acetate (column B). In column A, after about 600 pore volume exchanges (PVEs), VC started to disappear and reached almost zero VC recovery in the effluent after 1000 PVEs. No formation of ethene was observed. In column B, effluent VC was almost always only a fraction of influent VC. Formation of ethene was observed after 800 PVEs and started to become an important degradation product after 1550 PVEs. However, ethene was never observed in stoichiometric amounts compared with disappeared VC. The average stable isotope enrichment factor for VC disappearance in column A was determined to be -4.3‰. In column B, the isotope enrichment factor shifted from -10.7 to -18.5‰ concurrent with an increase in ethene production. Batch microcosms inoculated with column material showed similar isotope enrichment factors as the column microcosms. These results indicated that two degradation processes occurred, one in column A and two in parallel in column B with increasing importance of reductive dechlorination with time. This study suggests that in addition to reductive dechlorination, other degradation processes such as anaerobic oxidation should be taken into account when evaluating natural attenuation of VC and that isotope analysis can help to differentiate between different pathways of VC removal. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

The effect of guar gum and fiber-enriched wheat bran on gastric emptying of a semisolid meal in healthy subjects.

PubMed

Rydning, A; Berstad, A; Berstad, T; Hertzenberg, L

1985-04-01

The effect of physiological doses of guar gum (Guarem), 5 g, and fiber-enriched wheat bran (Fiberform), 10.5 g, on gastric emptying was studied by two different methods in healthy subjects: by a simple isotope localization monitor placed over the upper part of the abdomen and by gamma camera. The fiber preparations were added to a semisolid meal consisting of wheatmeal porridge and juice, using technetium-99 DTPA as a marker. The gamma camera showed no effect of fiber on gastric emptying. The isotope localization monitor, however, indicated that Fiberform prevented a postprandial accumulation of the meal within the upper part of the stomach. The simple isotope localization monitor cannot be recommended for measurements of gastric emptying.

Proteomic-based stable isotope probing reveals taxonomically Distinct Patterns in Amino Acid Assimilation by Coastal Marine Bacterioplankton

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

Bryson, Samuel; Li, Zhou; Pett-Ridge, Jennifer

Heterotrophic marine bacterioplankton are a critical component of the carbon cycle, processing nearly a quarter of annual global primary production, yet defining how substrate utilization preferences and resource partitioning structure these microbial communities remains a challenge. In this study, we utilized proteomics-based stable isotope probing (proteomic SIP) to characterize the assimilation of amino acids by coastal marine bacterioplankton populations. We incubated microcosms of seawater collected from Newport, OR and Monterey Bay, CA with 1 M 13C-amino acids for 15 and 32 hours. Subsequent analysis of 13C incorporation into protein biomass quantified the frequency and extent of isotope enrichment for identifiedmore » proteins. Using these metrics we tested whether amino acid assimilation patterns were different for specific bacterioplankton populations. Proteins associated with Rhodobacterales and Alteromonadales tended to have a significantly high number of tandem mass spectra from 13C-enriched peptides, while Flavobacteriales and SAR11 proteins generally had significantly low numbers of 13C-enriched spectra. Rhodobacterales proteins associated with amino acid transport and metabolism had an increased frequency of 13C-enriched spectra at time-point 2, while Alteromonadales ribosomal proteins were 13C- enriched across time-points. Overall, proteomic SIP facilitated quantitative comparisons of dissolved free amino acids assimilation by specific taxa, both between sympatric populations and between protein functional groups within discrete populations, allowing an unprecedented examination of population-level metabolic responses to resource acquisition in complex microbial communities.« less

Proteomic-based stable isotope probing reveals taxonomically Distinct Patterns in Amino Acid Assimilation by Coastal Marine Bacterioplankton

DOE PAGES

Bryson, Samuel; Li, Zhou; Pett-Ridge, Jennifer; ...

2016-04-26

Heterotrophic marine bacterioplankton are a critical component of the carbon cycle, processing nearly a quarter of annual global primary production, yet defining how substrate utilization preferences and resource partitioning structure these microbial communities remains a challenge. In this study, we utilized proteomics-based stable isotope probing (proteomic SIP) to characterize the assimilation of amino acids by coastal marine bacterioplankton populations. We incubated microcosms of seawater collected from Newport, OR and Monterey Bay, CA with 1 M 13C-amino acids for 15 and 32 hours. Subsequent analysis of 13C incorporation into protein biomass quantified the frequency and extent of isotope enrichment for identifiedmore » proteins. Using these metrics we tested whether amino acid assimilation patterns were different for specific bacterioplankton populations. Proteins associated with Rhodobacterales and Alteromonadales tended to have a significantly high number of tandem mass spectra from 13C-enriched peptides, while Flavobacteriales and SAR11 proteins generally had significantly low numbers of 13C-enriched spectra. Rhodobacterales proteins associated with amino acid transport and metabolism had an increased frequency of 13C-enriched spectra at time-point 2, while Alteromonadales ribosomal proteins were 13C- enriched across time-points. Overall, proteomic SIP facilitated quantitative comparisons of dissolved free amino acids assimilation by specific taxa, both between sympatric populations and between protein functional groups within discrete populations, allowing an unprecedented examination of population-level metabolic responses to resource acquisition in complex microbial communities.« less

High-throughput simultaneous determination of plasma water deuterium and 18-oxygen enrichment using a high-temperature conversion elemental analyzer with isotope ratio mass spectrometry.

PubMed

Richelle, M; Darimont, C; Piguet-Welsch, C; Fay, L B

2004-01-01

This paper presents a high-throughput method for the simultaneous determination of deuterium and oxygen-18 (18O) enrichment of water samples isolated from blood. This analytical method enables rapid and simple determination of these enrichments of microgram quantities of water. Water is converted into hydrogen and carbon monoxide gases by the use of a high-temperature conversion elemental analyzer (TC-EA), that are then transferred on-line into the isotope ratio mass spectrometer. Accuracy determined with the standard light Antartic precipitation (SLAP) and Greenland ice sheet precipitation (GISP) is reliable for deuterium and 18O enrichments. The range of linearity is from 0 up to 0.09 atom percent excess (APE, i.e. -78 up to 5725 delta per mil (dpm)) for deuterium enrichment and from 0 up to 0.17 APE (-11 up to 890 dpm) for 18O enrichment. Memory effects do exist but can be avoided by analyzing the biological samples in quintuplet. This method allows the determination of 1440 samples per week, i.e. 288 biological samples per week. Copyright 2004 John Wiley & Sons, Ltd.

Charge radii and electromagnetic moments of At-211195

NASA Astrophysics Data System (ADS)

Cubiss, J. G.; Barzakh, A. E.; Seliverstov, M. D.; Andreyev, A. N.; Andel, B.; Antalic, S.; Ascher, P.; Atanasov, D.; Beck, D.; Bieroń, J.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Derkx, X.; De Witte, H.; Elseviers, J.; Fedorov, D. V.; Fedosseev, V. N.; Fritzsche, S.; Gaffney, L. P.; George, S.; Ghys, L.; Heßberger, F. P.; Huyse, M.; Imai, N.; Kalaninová, Z.; Kisler, D.; Köster, U.; Kowalska, M.; Kreim, S.; Lane, J. F. W.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Marsh, B. A.; Mitsuoka, S.; Molkanov, P. L.; Nagame, Y.; Neidherr, D.; Nishio, K.; Ota, S.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Revill, J. P.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Sandhu, K.; Schweikhard, L.; Sels, S.; Truesdale, V. L.; Van Beveren, C.; Van den Bergh, P.; Wakabayashi, Y.; Van Duppen, P.; Wendt, K. D. A.; Wienholtz, F.; Whitmore, B. W.; Wilson, G. L.; Wolf, R. N.; Zuber, K.

2018-05-01

Hyperfine-structure parameters and isotope shifts of At-211195 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α -decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At,199197, for which a significant difference in the charge radii for ground (9 /2- ) and isomeric (1 /2+ ) states has been observed.

Space-Based Solar Power As an Opportunity for Strategic Security: Phase 0 Architecture Feasibility Study

DTIC Science & Technology

2007-10-10

levitation ( MAGLEV ) followed by rocket,  airbreathing/airborne oxygen enrichment, as well as electromagnetic launch, hybrid launch to  tethers, and...to‐orbit (TSTO) rocket powered vertical launch horizontal landing  (VTHL) to  Maglev  assisted airbreathing or airborne oxygen enrichment horizontal...takeoff and landing  (HOTOL).  Further alternatives include gun launch (typically electromagnetic, or  MagLev ), a space  elevator, or a hybrid tether

Rb-Sr and Sm-Nd Studies of Olivine-Phyric Shergottites RBT 04262 and LAR 06319: Isotopic Evidence for Relationship to Enriched Basaltic Shergottites

NASA Technical Reports Server (NTRS)

Nyquist, L.E.; Shih, C.-Y.; Reese, Y.

2009-01-01

RBT 04262 and LAR 06319 are two Martian meteorites recently discovered in Antarctica. Both contain abundant olivines, and were classified as olivine-phyric shergottites. A detailed petrographic study of RBT 04262 suggested it should be reclassified as a lherzolitic shergottite. However, the moderately LREE-depleted REE distribution pattern indicated that it is closely related to enriched basaltic shergottites like Shergotty, Zagami, Los Angeles, etc. In earlier studies of a similarly olivinephyric shergottite NWA 1068 which contains 21% modal olivine, it was shown that it probably was produced from an enriched basaltic shergottite magma by olivine accumulation . As for LAR 06319, recent petrographic studies suggested that it is different from either lherzolitic shergottites or the highly LREE-depleted olivine-phyric shergottites. We performed Rb-Sr and Sm-Nd isotopic analyses on RBT 04262 and LAR 06319 to determine their crystallization ages and Sr and Nd isotopic signatures, and to better understand the petrogenetic relationships between them and other basaltic, lherzolitic and depleted olivine-phyric shergottites.

Measurement of stable isotopic enrichment and concentration of long-chain fatty acyl-carnitines in tissue by HPLC-MS.

PubMed

Sun, Dayong; Cree, Melanie G; Zhang, Xiao-Jun; Bøersheim, Elisabet; Wolfe, Robert R

2006-02-01

We have developed a new method for the simultaneous measurements of stable isotopic tracer enrichments and concentrations of individual long-chain fatty acyl-carnitines in muscle tissue using ion-pairing high-performance liquid chromatography-electrospray ionization quadrupole mass spectrometry in the selected ion monitoring (SIM) mode. Long-chain fatty acyl-carnitines were extracted from frozen muscle tissue samples by acetonitrile/methanol. Baseline separation was achieved by reverse-phase HPLC in the presence of the volatile ion-pairing reagent heptafluorobutyric acid. The SIM capability of a single quadrupole mass analyzer allows further separation of the ions of interest from the sample matrixes, providing very clean total and selected ion chromatograms that can be used to calculate the stable isotopic tracer enrichment and concentration of long-chain fatty acyl-carnitines in a single analysis. The combination of these two separation techniques greatly simplifies the sample preparation procedure and increases the detection sensitivity. Applying this protocol to biological muscle samples proves it to be a very sensitive, accurate, and precise analytical tool.

Isotope ratios of trace elements in samples from human nutrition studies determined by TIMS and ICP-MS: precision and accuracy compared.

PubMed

Turnlund, Judith R; Keyes, William R

2002-09-01

Stable isotopes are used with increasing frequency to trace the metabolic fate of minerals in human nutrition studies. The precision of the analytical methods used must be sufficient to permit reliable measurement of low enrichments and the accuracy should permit comparisons between studies. Two methods most frequently used today are thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to compare the two methods. Multiple natural samples of copper, zinc, molybdenum, and magnesium were analyzed by both methods to compare their internal and external precision. Samples with a range of isotopic enrichments that were collected from human studies or prepared from standards were analyzed to compare their accuracy. TIMS was more precise and accurate than ICP-MS. However, the cost, ease, and speed of analysis were better for ICP-MS. Therefore, for most purposes, ICP-MS is the method of choice, but when the highest degrees of precision and accuracy are required and when enrichments are very low, TIMS is the method of choice.

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

Ozone isotope measurements in the stratosphere

NASA Technical Reports Server (NTRS)

Mauersberger, K.

1987-01-01

Mass spectrometer measurements of ozone made during two balloon flights included its heavy isotopes at mass 49 and 50. Both flights were flown during the day and during summer from Palestine, TX. At float altitudes above 42 km the enrichments in heavy ozone were 41 percent and 23 percent, respectively. The enrichment appears to be mass independent since, at high altitudes, both 49 and 50 show the same enhancement. During the descent the enrichment in heavy ozone decreased, faster during the first flight than during the second, reaching values between 15 and 20 percent above 30 km. Near and below this altitude another increase is observed. During a night flight, previously reported, an enhancement in heavy ozone of over 40 percent at 32 km was found, decreasing both toward higher and lower altitudes.

New Hafnium Isotope and Trace Element Constraints on the Role of a Plume in Genesis of the Eastern Snake River Plain Basalts, Idaho

NASA Astrophysics Data System (ADS)

Taylor, R. D.; Reid, M. R.; Blichert-Toft, J.

2009-12-01

Bimodal volcanism associated with the eastern Snake River Plain (ESRP)-Yellowstone Plateau province has persisted since approximately 16 Ma. A time-transgressive track of rhyolitic eruptions which young progressively to the east and parallel the motion of the North American plate are overlain by younger basalts with no age progression. Interpretations for the origin of these basalts range from a thermo-chemical mantle plume to incipient melting of the shallow upper mantle, and remain controversial. The enigmatic ESRP basalts are characterized by high 3He/4He, diagnostic of a plume source, but also by lithophile radiogenic isotope signatures that are more enriched than expected for plume-derived OIBs. These features could possibly be caused by isotopic decoupling associated with shallow melting of a hybridized upper mantle, or derivation from an atypical mantle plume, or both by way of mixing. New Hf isotope and trace element data further constrain potential sources for the ESRP basalts. Their Hf isotopic signatures (ɛHf = +0.1 to -5.8) are moderately enriched and consistently fall above or in the upper part of the field of OIBs, with similar Nd isotope signatures (ɛNd = -2.0 to -5.8), indicating a source with high time-integrated Lu/Hf compared with Sm/Nd. The isotopic compositions of the basalts lie between those of Archean SCML and a more depleted end-member source, suggestive of contributions from at least two sources. The grouping of isotopic characteristics is compact compared to other regional volcanism, implying that the hybridization process is highly reproducible within the ESRP. Minor localized differences in isotopic composition may signify local variations in the relative proportions of the end-members. Trace element patterns also support genesis of the ESRP basalts from an enriched source. Our data detect evidence of deeper contributions derived from the garnet-stability field, and a greater affinity of the trace element signatures to plume sources than to sources in the mantle lithosphere. The Hf isotope and trace element characteristics of the ESRP basalts thus support a model of derivation from a deep mantle plume with additional melt contributions and isotopic overprinting from SCML.

Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

PubMed

Pramann, Axel; Rienitz, Olaf

2016-06-07

A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) < 1 × 10(-9). This study presents a clear dependence of the uncertainty urel(M(Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram.

187Os-186Os and He Isotope Systematics of Iceland Picrites

NASA Astrophysics Data System (ADS)

Brandon, A. D.; Brandon, A. D.; Graham, D.; Gautason, B.

2001-12-01

Iceland is one of the longest-lived modern plumes, and seismic imaging supports a model where the roots of this plume are at the base of the lower mantle. Hence, Os isotopic data for lavas from this plume are ideal for further testing the role of core-mantle chemical exchange at the site of plume generation in the lower mantle, and for addressing the origin of Os-He isotopic variation in plumes. Recent work has shown that lavas from some plume systems (Hawaii, Noril'sk-Siberia, Gorgona) show coupled enrichments in 186Os/188Os and 187Os/188Os, not observed in upper mantle materials including abyssal peridotites. Picrites from Hawaii display a positive correlation between 186Os/188Os and He isotopes (R/Ra), where range in 186Os/188Os of 0.119834+/-28 to 0.1198475+/-29 and corresponding R/Ra from +7 to +25. These systematics are consistent with a lower mantle source for the radiogenic 186Os signal in the Hawaiian plume. The coupled Os enrichments in these plumes has been attributed to core-mantle chemical exchange, consistent with generation of the Hawaiian plume at the base of the lower mantle in D". Other potentially viable models await additional scrutiny. New He isotope and high precision 186Os/188Os and 187Os/188Os measurements for Iceland picrites show unique systematics compared to Hawaii. These picrites have 187Os/188Os ranging from 0.1297 to 0.1381 and R/Ra of +9 to +18, with generally higher R/Ra correlating with higher 187Os/188Os. Unlike the Hawaiian picrites from Hualalai and Loihi, which have coupled enrichments in 186Os/188Os and 187Os/188Os, the Iceland picrites show no enrichment 186Os/188Os - 0.1198363+/-28 (2s, n=14). Such Os-He isotopic variations require one end-member source that has high R/Ra, coupled with a long term elevated Re/Os and Pt/Os similar to that of the upper mantle. These systematics are inconsistent with either known upper mantle materials or those purported for ancient recycled slabs and may be a previously unidentified component in the lower mantle.

Low-Energy Sputtering Studies of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1999-01-01

Sputtering of boron nitride with xenon ions was investigated using secondary ion (SIMS) and secondary neutral (SNMS) mass spectrometry. The ions generated from the ion gun were incident on the target at an angle of 50' with respect to the surface'normal. The energy of ions ranged from 100 eV to 3 keV. A flood electron gun was used to neutralize the positive charge build-up on the target surface. The intensities of sputtered neutral and charged particles, including single atoms, molecules, and clusters, were measured as a function of ion energy. Positive SIMS spectra were dominated by the two boron isotopes whereas BN- and B- were the two major constituents of the negative SIMS spectra. Nitrogen could be detected only in the SNMS spectra. The intensity-energy curves of the sputtered particles were similar in shape. The knees in P-SIMS and SNMS intensity-energy curves appear at around I keV which is significantly higher that 100 to 200 eV energy range at which knees appear in the sputtering of medium and heavy elements by ions of argon and xenon. This difference in the position of the sputter yield knee between boron nitride and heavier targets is due to the reduced ion energy differences. The isotopic composition of secondary ions of boron were measured by bombarding boron nitride with xenon ions at energies ranging from 100 eV to 1.5 keV using a quadrupole mass spectrometer. An ion gun was used to generate the ion beam. A flood electron gun was used to neutralize the positive charge buildup on the target surface. The secondary ion flux was found to be enriched in heavy isotopes at lower incident ion energies. The heavy isotope enrichment was observed to decrease with increasing primary ion energy. Beyond 350 eV, light isotopes were sputtered preferentially with the enrichment increasing to an asymptotic value of 1.27 at 1.5 keV. The trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

N-C isotopic investigation of a zeolite-amended agricultural field

NASA Astrophysics Data System (ADS)

Ferretti, Giacomo; Natali, Claudio; Faccini, Barbara; Di Giuseppe, Dario; Bianchini, Gianluca; Coltorti, Massimo

2016-04-01

In this study, a C and N isotopic investigation in the soil-plant system of the ZeoLIFE project experimental field have been carried out. Since many years, natural and NH4-enriched zeolites have been used as soil amendant in agricultural context in order to reduce N losses, increase NUE (Nitrogen Use Efficiency) and crop yield. Nevertheless up to now there are no studies that, using the stable isotopes approach, highlighted the interaction between zeolites and plants in agricultural systems. The main aims of this study is to verify if natural zeolites amendment can enhance chemical fertilization efficiency and if N transfer from NH4-enriched zeolites to plants really occurs. Plants grown following traditional cultivation methods (with no zeolite addition) and plants grown on soils amended with natural and NH4-enriched zeolites (the latter obtained after mixing with pig-slurry with a very high 15N) were compared for two cultivation cycles (maize and wheat). As widely known, plants grown under conventional farming systems (use of chemical fertilizers as urea) and plants grown under organic farming can be discriminated by the isotopic signatures of plant tissues. For both years the main results of the study reveals that plants grown on plots amended with natural zeolites generally have their nitrogen isotopic signature more similar to that of the chemical fertilizers employed during the cultivation with respect to the plants cultivated in the non-amended plot. This suggests an enhanced N uptake by the plant from this specific N source with respect to the non-amended plot. On the other hand, plants grown on NH4-enriched zeolites registered a higher 15N, approaching the pig-slurry isotopic signature, confirming that this material can constitute an N pool for plants at least for two cultivation cycles. The distinct agricultural practices seem to be reflected in the plant physiology as recorded by the carbon discrimination factor (13C) which generally increases in plots amended with natural zeolites indicating better water/nutrient conditions. At similar N availability it seems that plant prefer to use natural N from pig slurry instead of using that coming from chemical fertilizers.

Combustion influences on natural abundance nitrogen isotope ratio in soil and plants following a wildfire in a sub-alpine ecosystem.

PubMed

Huber, Edith; Bell, Tina L; Adams, Mark A

2013-11-01

This before-and-after-impact study uses the natural abundance N isotope ratio (δ(15)N) to investigate the effects of a wildfire on sub-alpine ecosystem properties and processes. We measured the (15)N signatures of soil, charred organic material, ash and foliage in three sub-alpine plant communities (grassland, heathland and woodland) in south-eastern Australia. Surface bulk soil was temporarily enriched in (15)N immediately after wildfire compared to charred organic material and ash in all plant communities. We associated the enrichment of bulk soil with fractionation of N during combustion and volatilization of N, a process that also explains the sequential enrichment of (15)N of unburnt leaves > ash > charred organic material in relation to duration and intensity of heating. The rapid decline in (15)N of bulk soil to pre-fire values indicates that depleted ash, containing considerable amounts of total N, was readily incorporated into the soil. Foliar δ(15)N also increased with values peaking 1 year post-fire. Foliar enrichment was foremost coupled with the release of enriched NH4(+) into the soil owing to isotopic discrimination during volatilization of soluble N and combustion of organic material. The mode of post-fire regeneration influenced foliar (15)N enrichment in two species indicating use of different sources of N following fire. The use of natural abundance of (15)N in soil, ash and foliage as a means of tracing transformation of N during wildfire has established the importance of combustion products as an important, albeit temporary source of inorganic N for plants regenerating after wildfire.

Application of a Boson Expansion Formalism Based on the Random Phase Approximation to Samarium Isotopes

NASA Astrophysics Data System (ADS)

Jamaluddin, Muzhar Bin

The Boson Expansion Theory of Kishimoto and Tamura has proved to be very successful in describing quadrupole collective motions in even-even nuclei. This theory, however, involves a complicated transformation from the Tamm-Dancoff phonons to the phonons of the Random Phase Approximation. In this thesis a Boson Expansion formalism, derived directly from the Random Phase Approximation and set forth by Pedracchi and Tamura, is used to derive the boson forms of the nuclear Hamiltonian and the electromagnetic transition operator. Detailed discussions of the formalism of Pedrocchi and Tamura and its extension needed to perform realistic calculations are presented. The technique used to deriving the boson forms and the formulae used in the calculations are also given a thorough treatment to demonstrate the simplicity of this approach. Finally, the theory is tested by applying it to calculate the energy levels and some electromagnetic properties of the Samarium isotopes. The results show that the present theory is capable of describing the range of behavior from a vibrational to a rotational character of the Samarium isotopes as good as the previous theory.

Kinetic isotopic fractionation and the origin of HDO and CH3D in the solar system

NASA Technical Reports Server (NTRS)

Yung, Yuk L.; Wen, Jun-Shan; Friedl, Randall R.; Pinto, Joseph P.; Bayes, Kyle D.

1988-01-01

It is suggested that photochemical enrichment processes driven by stellar UV emissions could result in a large deuterium fractionation of water and methane relative to H2 in the primitive solar nebula. These enrichment processes could have profoundly influenced the isotopic content of water in the terrestrial planets, if a large fraction of their volatiles had been added by impacts of meteorites and comets formed in the outer parts of the solar nebula. Efficient mixing could have exposed the material in the interior of the solar nebula to starlight.

Relationships between the stable isotopic signatures of living and fossil foraminifera in Monterey Bay, California

NASA Astrophysics Data System (ADS)

Martin, Jonathan B.; Day, Shelley A.; Rathburn, Anthony E.; Perez, M. Elena; Mahn, Chris; Gieskes, Joris

2004-04-01

Fossil foraminifera are critical to paleoceanographic reconstructions including estimates of past episodes of methane venting. These reconstructions rely on benthic foraminifera incorporating and retaining unaltered the ambient isotopic compositions of pore fluids and bottom waters. Comparisons are made here of isotopic compositions of abundant live and fossil foraminifera (Uvigerina peregrina, Epistominella pacifica, Bulimina mexicana, and Globobulimina pacifica) collected in Monterey Bay, CA from two cold seeps (Clam Flats and Extrovert Cliffs) and from sediments ˜5 m outside of the Clam Flats seep. Clam Flats has steep δ13CDIC gradients (to <-45‰), but DIC at Extrovert Cliffs is less enriched in 12C (to approximately -22‰). Oxygen isotope values of fossil foraminifera at Clam Flats are ˜1.5‰ enriched in 18O over the living foraminifera, as well as those of both live and fossil foraminifera at Extrovert Cliffs, suggesting they may have lived during the last glacial maximum. Statistical comparisons (Student's t and Kolmogorov-Smirnov tests) of δ13C and δ18O values indicate that live and fossil foraminifera come from different populations at both Clam Flats and Extrovert Cliffs. At Clam Flats, the difference appears to result from alteration enriching some fossil foraminifera in 12C over live foraminifera. At Extrovert Cliffs, the fossil foraminifera are enriched in 13C over the live foraminifera, suggesting they lived prior to the onset of venting and thus that venting began recently. The short time of venting at Extrovert Cliffs may be responsible for the less alteration there compared with Clam Flats. These results indicate that preservation of foraminifera is likely to be poor within long-lived cold seeps, but that foraminifera living in the surrounding sediment may incorporate and preserve broad basin-wide changes in isotopic compositions of the ambient water.

Crystallization history of enriched shergottites from Fe and Mg isotope fractionation in olivine megacrysts

NASA Astrophysics Data System (ADS)

Collinet, Max; Charlier, Bernard; Namur, Olivier; Oeser, Martin; Médard, Etienne; Weyer, Stefan

2017-06-01

Martian meteorites are the only samples available from the surface of Mars. Among them, olivine-phyric shergottites are basalts containing large zoned olivine crystals with highly magnesian cores (Fo 70-85) and rims richer in Fe (Fo 45-60). The Northwest Africa 1068 meteorite is one of the most primitive "enriched" shergottites (high initial 87Sr/86Sr and low initial ε143Nd). It contains olivine crystals as magnesian as Fo 77 and is a major source of information to constrain the composition of the parental melt, the composition and depth of the mantle source, and the cooling and crystallization history of one of the younger magmatic events on Mars (∼180 Ma). In this study, Fe-Mg isotope profiles analyzed in situ by femtosecond-laser ablation MC-ICP-MS are combined with compositional profiles of major and trace elements in olivine megacrysts. The cores of olivine megacrysts are enriched in light Fe isotopes (δ56FeIRMM-14 = -0.6 to -0.9‰) and heavy Mg isotopes (δ26MgDSM-3 = 0-0.2‰) relative to megacryst rims and to the bulk martian isotopic composition (δ56Fe = 0 ± 0.05‰, δ26Mg = -0.27 ± 0.04‰). The flat forsterite profiles of megacryst cores associated with anti-correlated fractionation of Fe-Mg isotopes indicate that these elements have been rehomogenized by diffusion at high temperature. We present a 1-D model of simultaneous diffusion and crystal growth that reproduces the observed element and isotope profiles. The simulation results suggest that the cooling rate during megacryst core crystallization was slow (43 ± 21 °C/year), and consistent with pooling in a deep crustal magma chamber. The megacryst rims then crystallized 1-2 orders of magnitude faster during magma transport toward the shallower site of final emplacement. Megacryst cores had a forsterite content 3.2 ± 1.5 mol% higher than their current composition and some were in equilibrium with the whole-rock composition of NWA 1068 (Fo 80 ± 1.5). NWA 1068 composition is thus close to a primary melt (i.e. in equilibrium with the mantle) from which other enriched shergottites derived.

Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

NASA Astrophysics Data System (ADS)

Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

2015-07-01

Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of heavy Zn from the soil to cell wall remains and release of light Zn to the soil. Overall, this study provides a complete overview of Zn cycling in an urban wetland soil-plant system, and describes several changes in Zn speciation with Zn isotopic fractionation processes in a complex system.

On the trophic ecology of Gammaridea (Crustacea: Amphipoda) in coastal waters: A European-scale analysis of stable isotopes data

NASA Astrophysics Data System (ADS)

Mancinelli, Giorgio

2012-12-01

Gammaridean amphipods are found throughout a diverse range of coastal and brackish environments and are generally considered macrophagous herbivores/detritivores. While predation and cannibalism have been shown to be common in freshwater species, motivating a revision of the group functional role, only qualitative information is available on marine Gammaridea. In this study, a survey was conducted of the available literature on stable C and N isotopic signatures of macrophagous, fully aquatic Gammaridea and their potential basal resources in European brackish and coastal environments. The contribution of intra- and inter-specific predation to the signatures of gammarideans was verified by a mixing model procedure where the diet-tissue enrichment constant was not set a priori. Specifically, for each study included in the survey the minimum and maximum diet-tissue nitrogen enrichment factors (Δ15Nmin and Δ15Nmax) providing a non-zero solution were calculated for a range of carbon enrichment factors, assuming that both metrics would increasingly differ from the values expected for a single trophic level as predation and/or cannibalism increased in the diet of the consumer. The minimum enrichment factors Δ15Nmin estimated for a Δ13C of -2.6‰ and +0.5‰ were found to be independent from resource-related artefacts and provided the highest number of successful model runs. Δ15Nmin values were consistent with a diet based on living or decaying primary producers and not compatible with cannibalism or intra-guild predation. However, they showed a bimodal distribution and were on average far below the range found in the literature, matching the enrichment factors of gammarideans measured under laboratory conditions. These results are discussed considering the interaction of the distinctive isotopic features of basal resources in coastal habitats and the biology and ecology of gammaridean amphipods. Particular emphasis is placed on the high variability of nitrogen enrichment factors, and on their crucial role in attaining reliable results from isotopic models used for food web studies.

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

PubMed

van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

2014-06-01

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

An assessment of the isotopic (2H/18O) integrity of water samples collected and stored by unattended precipitation totalizers

NASA Astrophysics Data System (ADS)

Terzer, Stefan; Wassenaar, Leonard I.; Douence, Cedric; Araguas-Araguas, Luis

2016-04-01

The IAEA-WMO Global Network of Isotopes in Precipitation (GNIP) provides worldwide δ18O and δ2H data for numerous hydrological and climatological studies. The traditional GNIP sample collection method relies on weather station operators to accumulate precipitation obtained from manual rain gauges. Over the past decades, widespread weather station automatization resulted in the increased use of unattended precipitation totalizers that accumulate and store the rainwater in the field for up to one month. Several low-tech measures were adopted to prevent in situ secondary evaporative isotopic enrichment (SEE) of totalized water samples (i.e. disequilibrium isotopic fractionation after precipitation is stored in the collection device). These include: (a) adding a 0.5-1 cm floating layer of paraffin oil to the totalizer bottle, (b) using an intake tube leading from the collection funnel and submerged to the bottom of the totalizer bottle, or (c) placing a table tennis ball in the funnel aiming to reduce evaporation of the collected water from the receiving bottle to the atmosphere. We assessed the isotopic integrity of stored rainwater samples for three totalizers under controlled settings: each aforementioned totalizer was filled with a 100 or 500 mL of isotopically known water and installed in the field with the intake funnels sheltered to prevent rainwater collection. Potential evapotranspiration (PET) was obtained from on-site meteorological recordings. Stored evaporative loss from each totalizer was evaluated on a monthly basis; gravimetrically and by analysing δ18O and δ2H of the stored water, for a period of 6 months and a cumulative PET of ˜500 mm. The gravimetric and isotope results revealed that for smaller water volumes (100 ml, corresponding to ca. 5 mm of monthly precipitation), negligible isotope enrichment (δ18O) was observed in the paraffin-oil based totalizer, whereas unacceptable evaporative isotope effects were observed for the ball-in-funnel collector. For the submerged-tube sampler, the evaporative effect depended on the amount of stored water: 100 ml showed unacceptable isotopic enrichment, whereas the SEE of 500 ml stored water was acceptable. These data allowed us to estimate the impact of secondary evaporative enrichment on a device-specific basis as a function of PET. Based on global PET grids (e.g. CGIAR data), and benchmarking the expected SEE against the reasonable uncertainty of isotope spectrometry (< ±0.1‰ for δ18O), these findings reveal the most suitable totalizer device for any given climatic condition. Under extreme conditions (e.g. high aridity, little precipitation vs. high PET), a paraffin-oil based rain totalizer is most appropriate for monthly collections. Submerged-tube samplers may be considered if either a higher frequency of collection were possible, or monthly under pluvial/temperate climate conditions. The use of ball-in-funnel type totalizers are not recommended at all, unless samples could be collected on a daily basis.

Plant family identity distinguishes patterns of carbon and nitrogen stable isotope abundance and nitrogen concentration in mycoheterotrophic plants associated with ectomycorrhizal fungi.

PubMed

Hynson, Nicole A; Schiebold, Julienne M-I; Gebauer, Gerhard

2016-09-01

Mycoheterotrophy entails plants meeting all or a portion of their carbon (C) demands via symbiotic interactions with root-inhabiting mycorrhizal fungi. Ecophysiological traits of mycoheterotrophs, such as their C stable isotope abundances, strongly correlate with the degree of species' dependency on fungal C gains relative to C gains via photosynthesis. Less explored is the relationship between plant evolutionary history and mycoheterotrophic plant ecophysiology. We hypothesized that the C and nitrogen (N) stable isotope compositions, and N concentrations of fully and partially mycoheterotrophic species differentiate them from autotrophs, and that plant family identity would be an additional and significant explanatory factor for differences in these traits among species. We focused on mycoheterotrophic species that associate with ectomycorrhizal fungi from plant families Ericaceae and Orchidaceae. Published and unpublished data were compiled on the N concentrations, C and N stable isotope abundances (δ(13)C and δ(15)N) of fully (n = 18) and partially (n = 22) mycoheterotrophic species from each plant family as well as corresponding autotrophic reference species (n = 156). These data were used to calculate site-independent C and N stable isotope enrichment factors (ε). Then we tested for differences in N concentration, (13)C and (15)N enrichment among plant families and trophic strategies. We found that in addition to differentiating partially and fully mycoheterotrophic species from each other and from autotrophs, C and N stable isotope enrichment also differentiates plant species based on familial identity. Differences in N concentrations clustered at the plant family level rather than the degree of dependency on mycoheterotrophy. We posit that differences in stable isotope composition and N concentrations are related to plant family-specific physiological interactions with fungi and their environments. © The Author 2016. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Geochemistry of oceanic carbonatites compared with continental carbonatites: mantle recycling of oceanic crustal carbonate

NASA Astrophysics Data System (ADS)

Hoernle, Kaj; Tilton, George; Le Bas, Mike; Duggen, Svend; Garbe-Schönberg, Dieter

Major and trace element and Sr-Nd-Pb-O-C isotopic compositions are presented for carbonatites from the Cape Verde (Brava, Fogo, Sáo Tiago, Maio and Sáo Vicente) and Canary (Fuerteventura) Islands. Carbonatites show pronounced enrichment in Ba, Th, REE, Sr and Pb in comparison to most silicate volcanic rocks and relative depletion in Ti, Zr, Hf, K and Rb. Calcio (calcitic)-carbonatites have primary (mantle-like) stable isotopic compositions and radiogenic isotopic compositions similar to HIMU-type ocean island basalts. Cape Verde carbonatites, however, have more radiogenic Pb isotope ratios (e.g. 206Pb/204Pb=19.3-20.4) than reported for silicate volcanic rocks from these islands (18.7-19.9 Gerlach et al. 1988; Kokfelt 1998). We interpret calcio-carbonatites to be derived from the melting of recycled carbonated oceanic crust (eclogite) with a recycling age of 1.6 Ga. Because of the degree of recrystallization, replacement of calcite by secondary dolomite and elevated ∂13C and ∂18O, the major and trace element compositions of the magnesio (dolomitic)-carbonatites are likely to reflect secondary processes. Compared with Cape Verde calcio-carbonatites, the less radiogenic Nd and Pb isotopic ratios and the negative Δ7/4 of the magnesio-carbonatites (also observed in silicate volcanic rocks from the Canary and Cape Verde Islands) cannot be explained through secondary processes or through the assimilation of Cape Verde crust. These isotopic characteristics require the involvement of a mantle component that has thus far only been found in the Smoky Butte lamproites from Montana, which are believed to be derived from subcontinental lithospheric sources. Continental carbonatites show much greater variation in radiogenic isotopic composition than oceanic carbonatites, requiring a HIMU-like component similar to that observed in the oceanic carbonatites and enriched components. We interpret the enriched components to be Phanerozoic through Proterozoic marine carbonate (e.g. limestone) recycled through shallow, subcontinental-lithospheric-mantle and deep, lower-mantle sources.

Geochemistry of oceanic carbonatites compared with continental carbonatites: mantle recycling of oceanic crustal carbonate

NASA Astrophysics Data System (ADS)

Hoernle, Kaj; Tilton, George; Le Bas, Mike; Duggen, Svend; Garbe-Schönberg, Dieter

2001-11-01

Major and trace element and Sr-Nd-Pb-O-C isotopic compositions are presented for carbonatites from the Cape Verde (Brava, Fogo, Sáo Tiago, Maio and Sáo Vicente) and Canary (Fuerteventura) Islands. Carbonatites show pronounced enrichment in Ba, Th, REE, Sr and Pb in comparison to most silicate volcanic rocks and relative depletion in Ti, Zr, Hf, K and Rb. Calcio (calcitic)-carbonatites have primary (mantle-like) stable isotopic compositions and radiogenic isotopic compositions similar to HIMU-type ocean island basalts. Cape Verde carbonatites, however, have more radiogenic Pb isotope ratios (e.g. 206Pb/204Pb=19.3-20.4) than reported for silicate volcanic rocks from these islands (18.7-19.9 Gerlach et al. 1988; Kokfelt 1998). We interpret calcio-carbonatites to be derived from the melting of recycled carbonated oceanic crust (eclogite) with a recycling age of 1.6 Ga. Because of the degree of recrystallization, replacement of calcite by secondary dolomite and elevated ∂13C and ∂18O, the major and trace element compositions of the magnesio (dolomitic)-carbonatites are likely to reflect secondary processes. Compared with Cape Verde calcio-carbonatites, the less radiogenic Nd and Pb isotopic ratios and the negative Δ7/4 of the magnesio-carbonatites (also observed in silicate volcanic rocks from the Canary and Cape Verde Islands) cannot be explained through secondary processes or through the assimilation of Cape Verde crust. These isotopic characteristics require the involvement of a mantle component that has thus far only been found in the Smoky Butte lamproites from Montana, which are believed to be derived from subcontinental lithospheric sources. Continental carbonatites show much greater variation in radiogenic isotopic composition than oceanic carbonatites, requiring a HIMU-like component similar to that observed in the oceanic carbonatites and enriched components. We interpret the enriched components to be Phanerozoic through Proterozoic marine carbonate (e.g. limestone) recycled through shallow, subcontinental-lithospheric-mantle and deep, lower-mantle sources.

Combined Li-He isotopes in Iceland and Jan Mayen basalts and constraints on the nature of the North Atlantic mantle

NASA Astrophysics Data System (ADS)

Magna, T.; Wiechert, U.; Stuart, F. M.; Halliday, A. N.; Harrison, D.

2011-02-01

Lithium (Li) isotopes are thought to provide a powerful proxy for the recycling of crustal material, affected by low temperature alteration, through the mantle. We present Li isotope compositions for basaltic volcanic rocks from Hengill, Iceland, and Jan Mayen in order to examine possible links between ocean island volcanism and recycled oceanic crust and to address recent suggestions that mantle 3He/ 4He is also related to recycling of ancient slabs. Basaltic glasses spanning a range of chemical enrichment from the Hengill fissure system define an inverse correlation between δ 7Li (3.8-6.9‰) and 3He/ 4He (12-20 RA). The high- 3He/ 4He basalts have low δ 18O as well as excess Eu and high Nb/U, but carry no Li isotope evidence of being the product of recycling of altered slab or wedge material. In fact, there is no clear correlation between Li or He isotopes on the one hand and any of the other fingerprints of recycled slab components. The low- 3He/ 4He samples do have elevated Nb/U, Sr/Nd, positive Eu anomalies and high δ 7Li (˜6.9‰), providing evidence of a cumulate-enriched source that could be part of an ancient altered ocean floor slab. Basalts from Jan Mayen are characterized by large degrees of enrichment in incompatible trace elements typical of EM-like basalts but have homogeneous δ 7Li typical of depleted mantle (3.9-4.7‰) providing evidence for a third mantle source in the North Atlantic. It appears that oceanic basalts can display a wide range in isotope and trace element compositions associated with recycled components whilst exhibiting no sign of modern surface-altered slab or wedge material from the Li isotope composition.

Formation of Neutron-Enriched Heavy and Superheavy Nuclei in Fusion Reactions

NASA Astrophysics Data System (ADS)

Karpov, A. V.; Rachkov, V. A.; Saiko, V. V.

2018-05-01

The formation of new isotopes of heavy and superheavy elements in the fusion of neutron-enriched projectiles with actinide targets is discussed. Cross sections for the formation of evaporation residues in fusion reactions is predicted for several combinations of colliding nuclei.

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

Visualizing Single Cell Biology: Nanosims Studies of Carbon and Nitrogen Metabolism in Diazotrophic Cyanobacteria

NASA Astrophysics Data System (ADS)

Pett-Ridge, J.; Finzi, J. A.; Capone, D. G.; Popa, R.; Nealson, K. H.; Ng, W.; Spormann, A. M.; Hutcheon, I. D.; Weber, P. K.

2007-12-01

Filamentous nitrogen fixing (diazotrophic) cyanobacteria are key players in global nutrient cycling, but the relationship between CO2- and N2-fixation and intercellular exchange of these elements remains poorly understood in many genera. These bacteria are faced with the challenge of isolating regions of N-fixation (O2 inhibited) and photosynthetic (O2 producing) activity. We used isotope labeling in conjunction with a high-resolution isotope and elemental mapping technique (NanoSIMS) to quantitatively describe 13C and 15N uptake and transport in two aquatic cyanobacteria grown on NaH13CO3 and 15N2. The technical challenges of tracing isotopes within individual bacteria can be overcome with high resolution Secondary Ion Mass Spectrometry (NanoSIMS). In NanoSIMS analysis, samples are sputtered with an energetic primary beam (Cs+, O-) liberating secondary ions that are separated by the mass spectrometer and detected in a suite of electron multipliers. Five isotopic species may be analyzed concurrently with spatial resolution as fine as 50nm. A high sensitivity isotope ratio 'map' can then be generated for the analyzed area. Using sequentially harvested cyanobacteria in conjunction with enriched H13CO3 and 15N2 incubations, we measured temporal enrichment patterns that evolve over the course of a day's growth and suggest tightly regulated changes in fixation kinetics. With a combination of TEM, SEM and NanoSIMS analyses, we also mapped the distribution of C, N and Mo (a critical nitrogenase co-factor) isotopes in intact cells. Our results suggest that NanoSIMS mapping of metal enzyme co-factors may be a powerful method of identifying physiological and morphological characteristics within individual bacterial cells, and could be used to provide a 3-dimensional context for more traditional analyses such as immunogold labeling. Finally, we resolved patterns of isotope enrichment at multiple spatial scales: sub-cellular variation, cell-cell differences along filaments, inter-species transfers (with Rhizobium epibionts), and within-cell depth profiles. Spatial enrichment patterns were correlated with morphological features evidenced in TEM images of microtomed filaments. These features indicate how 15N and 13C "hotspots" are dispersed throughout individual cells in different species, and may indicate isolated locations of increased N2 fixation, sites of amino acid/protein synthesis, or cyanophycin storage granules. This combination of Nano-Secondary Ion Mass Spectrometry (NanoSIMS) analysis and high resolution microscopy allows isotopic analysis to be linked to morphological features and holds great promise for fine-scale studies of bacteria metabolism.

Evaluation of carbon isotope fractionation during anaerobic reductive dehalogenation of chlorinated and brominated benzenes.

PubMed

Sohn, Seo Yean; Kuntze, Kevin; Nijenhuis, Ivonne; Häggblom, Max M

2018-02-01

Compound specific stable isotope analysis (CSIA) has been established as a useful tool to evaluate in situ biodegradation. Here, CSIA was used to determine microbial dehalogenation of chloro- and bromobenzenes in microcosms derived from Hackensack River sediments. Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) was used to measure carbon isotope fractionation during reductive dehalogenation of hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5-tetrachlorobenzene (TeCB), 1,2,3,5-tetrabromobenzene (TeBB), and 1,3,5-tribromobenzene (TriBB). Strong evidence of isotope fractionation coupled to dehalogenation was not observed in the substrate, possibly due to the low solubilities of the highly halogenated benzene substrates and a dilution of the isotope signal. Nonetheless, we could measure a depletion of the δ 13 C value in the dichlorobenzene product during dechlorination of HCB, the sequential depletion and enrichment of δ 13 C value for trichlorobenzene in TeCB dechlorinating cultures, and the enrichment of δ 13 C during debromination of TriBB. This indicates that a measurable isotope fractionation occurred during reductive dehalogenation of highly halogenated chloro- and bromobenzenes in aquatic sediments. Thus, although more quantitative measurements will be needed, the data suggests that CSIA may have application for monitoring in situ microbial reductive dehalogenation of highly halogenated benzenes. Copyright © 2017. Published by Elsevier Ltd.

Nitrogen isotopic components in the early solar system

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1994-01-01

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

Comparing isotope signatures of prey fish: does gut removal affect δ13C or δ15N?

USGS Publications Warehouse

Chipps, Steven R.; Fincel, Mark J.; VanDeHey, Justin A.; Wuestewald, Andrew

2011-01-01

Stable isotope analysis is a quick and inexpensive method to monitor the effects of food web changes on aquatic communities. Traditionally, whole specimens have been used when determining isotope composition of prey fish or age-0 recreational fishes. However, gut contents of prey fish could potentially alter isotope composition of the specimen, especially when recent foraging has taken place or when the gut contains non-assimilated material that would normally pass through fishes undigested. To assess the impacts of gut content on prey fish isotope signatures, we examined the differences in isotopic variation of five prey fish species using whole fish, whole fish with the gut contents removed, and dorsal muscle only. We found significant differences in both δ15N and δ13C between the three tissue treatments. In most cases, muscle tissue was enriched compared to whole specimens or gut-removed specimens. Moreover, differences in mean δ15N within a species were up to 2‰ among treatments. This would result in a change of over half a trophic position (TP) based on a 3.4‰ increase per trophic level. However, there were no apparent relationships between tissue isotope values in fish with increased gut fullness (more prey tissue present). We suggest that muscle tissue should be used as the standard tissue for determining isotope composition of prey fish or age-0 recreational fishes, especially when determining enrichment for mixing models, calculating TP, or constructing aquatic food webs.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

PubMed

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Nuclear volume effects in equilibrium stable isotope fractionations of mercury, thallium and lead

PubMed Central

Yang, Sha; Liu, Yun

2015-01-01

The nuclear volume effects (NVEs) of Hg, Tl and Pb isotope systems are investigated with careful evaluation on quantum relativistic effects via the Dirac’s formalism of full-electron wave function. Equilibrium 202Hg/198Hg, 205Tl/203Tl, 207Pb/206Pb and 208Pb/206Pb isotope fractionations are found can be up to 3.61‰, 2.54‰, 1.48‰ and 3.72‰ at room temperature, respectively, larger than fractionations predicted by classical mass-dependent isotope fractionations theory. Moreover, the NVE can cause mass-independent fractionations (MIF) for odd-mass isotopes and even-mass isotopes. The plot of vs. for Hg-bearing species falls into a straight line with the slope of 1.66, which is close to previous experimental results. For the first time, Pb4+-bearing species are found can enrich heavier Pb isotopes than Pb2+-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of 208Pb/206Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb2+-bearing species are trivial. Therefore, the large Pb fractionation changes provide a potential new tracer for redox conditions in young and closed geologic systems. The magnitudes of NVE-driven even-mass MIFs of Pb isotopes (i.e., ) and odd-mass MIFs (i.e., ) are almost the same but with opposite signs. PMID:26224248

Stability of the Orca Basin Brine Interface Determined Using Radium Isotopes

NASA Astrophysics Data System (ADS)

Peterson, R. N.; Peterson, L.; Montoya, J. P.; Joye, S. B.

2016-02-01

The Orca Basin is an intraslope basin in the northern continental slope of the Gulf of Mexico, and contains a deep (up to 220 m) anoxic, hypersaline brine lake. The brine interface extends from ocean salinity (at a water depth of 2125 m) to a constant salinity of 215 psu below a depth of 2250 m. This interface is considered to be among the most stable interfaces on the planet, and contains distinct zones of macrofaunal and microbial assemblages. The brine lake is supported by continued dissolution of exposed rock salt at an estimated rate of 0.5 million t/yr. Such dissolution of salt should serve as a source of radium isotopes, and given their range of half-lives, these isotopes can serve as unique proxies to the location and rate of salt dissolution into this basin. We have collected a series of radon and radium isotope profiles through this brine lake over the past 4 years, which allow us to assess the spatial and temporal stability of this interface. Throughout the brine lake, we observe strong enrichments in unsupported Ra-224, Rn-222, and Ra-226 in a 10 m thick zone near the base of the brine interface, between 2232 m and 2242 m. The strong enrichment in unsupported Ra-224 in this layer must be supported by a continuous source, presumably the dissolution of exposed salt rock. Various degrees of isotopic enrichment throughout the lake provide an assessment of the rates of lateral and vertical dispersion of salt and associated chemical constituents.

Preliminary Report on U-Th-Pb Isotope Systematics of the Olivine-Phyric Shergottite Tissint

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

2014-01-01

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions, and trace element abundances.. These correlations have been interpreted as indicating the presence of a reduced, incompatible-element- depleted reservoir and an oxidized, incompatible-element-rich reservoir. The former is clearly a depleted mantle source, but there has been a long debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former clearly requires the ancient martian crust to be the enriched source (crustal assimilation), whereas the latter requires a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and U-Th-Pb concentration analyses of the olivine-phyric shergottite Tissint because U-Th-Pb isotope systematics have been intensively used as a powerful radiogenic tracer to characterize old crust/sediment components in mantle- derived, terrestrial oceanic island basalts. The U-Th-Pb analyses are applied to sequential acid leaching fractions obtained from Tissint whole-rock powder in order to search for Pb isotopic source components in Tissint magma. Here we report preliminary results of the U-Th-Pb analyses of acid leachates and a residue, and propose the possibility that Tissint would have experienced minor assimilation of old martian crust.

Ratios of carbon isotopes in microbial lipids as an indicator of substrate usage.

PubMed

Abraham, W R; Hesse, C; Pelz, O

1998-11-01

The occurrence and abundance of microbial fatty acids have been used for the identification of microorganisms in microbial communities. However, these fatty acids can also be used as indicators of substrate usage. For this, a systematic investigation of the discrimination of the stable carbon isotopes by different microorganisms is necessary. We grew 11 strains representing major bacterial and fungal species with four different isotopically defined carbon sources and determined the isotope ratios of fatty acids of different lipid fractions. A comparison of the differences of delta13C values of palmitic acid (C16:0) with the delta13C values of the substrates revealed that the isotope ratio is independent of the growth stage and that most microorganisms showed enrichment of C16:0 with 13C when growing on glycerol. With the exception of Burkholderia gladioli, all microorganism showed depletion of 13C in C16:0 while incorporating the carbons of glucose, and most of them were enriched with 13C from mannose, with the exception of Pseudomonas fluorescens and the Zygomycotina. Usually, the glycolipid fractions are depleted in 13C compared to the phospholipid fractions. The delta13C pattern was not uniform within the different fatty acids of a given microbial species. Generally, tetradecanoic acid (C14:0) was depleted of 13C compared to palmitic acid (C16:0) while octadecanoic acid (C18:0) was enriched. These results are important for the calibration of a new method in which delta13C values of fatty acids from the environment delineate the use of bacterial substrates in an ecosystem.

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis.

PubMed

Thoma, Michael; Frentress, Jay; Tagliavini, Massimo; Scandellari, Francesca

2018-02-15

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2 ‰ for δ 2 H and 1 ‰ for δ 18 O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8 ‰ for δ 2 H and 4 ‰ for δ 18 O. In (3), PWS water was enriched relative to CE water by 3 ‰ for δ 2 H and 0.9 ‰ for δ 18 O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).

Environmental Isotope Characteristics of Landfill Leachates and Gases

USGS Publications Warehouse

Hackley, Keith C.; Liu, Chao-Li; Coleman, D.D.

1996-01-01

The isotopic characteristics of municipal landfill leachate and gases (carbon dioxide and methane) are unique relative to the aqueous and gaseous media in most other natural geologic environments. The ??13 C of the CO2 in landfills is significantly enriched in 13C, with values as high as +20??? reported. The ?? 13C and ??D values of the methane fall within a range of values representative of microbial methane produced primarily by the acetate-fermentation process. The ??D of landfill leachate is strongly enriched in deuterium, by approximately 30??? to nearly 60??? relative to local average precipitation values. This deuterium enrichment is undoubtedly due to the extensive production of microbial methane within the limited reservoir of a landfill. The concentration of the radiogenic isotopes, 14C and 3H, are significantly elevated in both landfill leachate and methane. The 14C values range between approximately 120 and 170 pMC and can be explained by the input of organic material that was affected by the increased 14C content of atmospheric CO2 caused by atmospheric testing of nuclear devices. The tritium measured in leachate, however, is often too high to be explained by previous atmospheric levels and must come from material buried within the landfill. The unique isotopic characteristics observed in landfill leachates and gases provide a very useful technique for confirming whether contamination is from a municipal landfill or some other local source.

Stable carbon and nitrogen isotope enrichment in primate tissues

PubMed Central

Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

2010-01-01

Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

D and 18O enrichment measurements in biological fluids in a continuous-flow elemental analyser with an isotope-ratio mass spectrometer using two configurations.

PubMed

Ripoche, N; Ferchaud-Roucher, V; Krempf, M; Ritz, P

2006-09-01

In doubly labelled water studies, biological sample enrichments are mainly measured using off-line techniques (equilibration followed by dual-inlet introduction) or high-temperature elemental analysis (HT-EA), coupled with an isotope-ratio mass spectrometer (IRMS). Here another continuous-flow method, (CF-EA/IRMS), initially dedicated to water, is tested for plasma and urine analyses. The elemental analyser configuration is adapted for each stable isotope: chromium tube for deuterium reduction and glassy carbon reactor for 18O pyrolysis. Before on-line conversion of water into gas, each matrix is submitted to a short and easy treatment, which is the same for the analysis of the two isotopes. Plasma is passed through centrifugal filters. Urine is cleaned with black carbon and filtered (0.45 microm diameter). Tested between 150 and 300 ppm in these fluids, the D/H ratio response is linear with good repeatability (SD<0.2 ppm) and reproducibility (SD<0.5 ppm). For 18O/16O ratios (from 2000 to 2200 ppm), the same repeatability is obtained with a between-day precision lower than 1.4 ppm. The accuracy on biological samples is validated by comparison to classical dual-inlet methods: 18O analyses give more accurate results. The data show that enriched physiological fluids can be successfully analysed in CF-EA/IRMS. Copyright (c) 2006 John Wiley & Sons, Ltd.

Using species-specific enriched stable isotopes to study the effect of fresh mercury inputs in soil-earthworm systems.

PubMed

Álvarez, C Rodríguez; Jiménez-Moreno, M; Bernardo, F J Guzmán; Martín-Doimeadios, R C Rodríguez; Nevado, J J Berzas

2018-01-01

The fate of mercury (Hg) in the soil-earthworm system is still far from being fully understood, especially regarding recurrent and challenging questions about the importance of the reactivity of exogenous Hg species. Thus, to predict the potential effect of Hg inputs in terrestrial ecosystems, it is necessary to evaluate separately the reactivity of the endogenous and exogenous Hg species and, for this purpose, the use of enriched stable isotope tracers is a promising tool. In the present work, earthworms (Lumbricus terrestris) were exposed to historically Hg contaminated soils from the Almadén mining district, Spain. The soils were either non-spiked, which contain only endogenous or native Hg naturally occurring in the soil, or spiked with isotopically enriched inorganic Hg ( 199 IHg), representing exogenous or spiked Hg apart from the native one. The differential reactivity of endogenous and exogenous Hg in the soil conditioned the processes of methylation, mobilization, and assimilation of inorganic Hg by earthworms. Both endogenous and exogenous Hg species also behave distinctly regarding their bioaccumulation in earthworms, as suggested by the bioaccumulation factors, being the endogenous methylmercury (MeHg) the species more readily bioaccumulated by earthworms and in a higher extent. To the best of our knowledge, this work demonstrates for the first time the potential of enriched stable isotopes to study the effects of fresh Hg inputs in soil-earthworm systems. The findings of this work can be taken as a case study on the dynamics of Hg species in complex terrestrial systems and open a new door for future experiments. Copyright © 2017 Elsevier Inc. All rights reserved.

ForCent model development and testing using the Enriched Background Isotope Study experiment

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

Parton, W.J.; Hanson, P. J.; Swanston, C.

The ForCent forest ecosystem model was developed by making major revisions to the DayCent model including: (1) adding a humus organic pool, (2) incorporating a detailed root growth model, and (3) including plant phenological growth patterns. Observed plant production and soil respiration data from 1993 to 2000 were used to demonstrate that the ForCent model could accurately simulate ecosystem carbon dynamics for the Oak Ridge National Laboratory deciduous forest. A comparison of ForCent versus observed soil pool {sup 14}C signature ({Delta} {sup 14}C) data from the Enriched Background Isotope Study {sup 14}C experiment (1999-2006) shows that the model correctly simulatesmore » the temporal dynamics of the {sup 14}C label as it moved from the surface litter and roots into the mineral soil organic matter pools. ForCent model validation was performed by comparing the observed Enriched Background Isotope Study experimental data with simulated live and dead root biomass {Delta} {sup 14}C data, and with soil respiration {Delta} {sup 14}C (mineral soil, humus layer, leaf litter layer, and total soil respiration) data. Results show that the model correctly simulates the impact of the Enriched Background Isotope Study {sup 14}C experimental treatments on soil respiration {Delta} {sup 14}C values for the different soil organic matter pools. Model results suggest that a two-pool root growth model correctly represents root carbon dynamics and inputs to the soil. The model fitting process and sensitivity analysis exposed uncertainty in our estimates of the fraction of mineral soil in the slow and passive pools, dissolved organic carbon flux out of the litter layer into the mineral soil, and mixing of the humus layer into the mineral soil layer.« less

ForCent Model Development and Testing using the Enriched Background Isotope Study (EBIS) Experiment

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

Parton, William; Hanson, Paul J; Swanston, Chris

The ForCent forest ecosystem model was developed by making major revisions to the DayCent model including: (1) adding a humus organic pool, (2) incorporating a detailed root growth model, and (3) including plant phenological growth patterns. Observed plant production and soil respiration data from 1993 to 2000 were used to demonstrate that the ForCent model could accurately simulate ecosystem carbon dynamics for the Oak Ridge National Laboratory deciduous forest. A comparison of ForCent versus observed soil pool 14C signature (? 14C) data from the Enriched Background Isotope Study 14C experiment (1999-2006) shows that the model correctly simulates the temporal dynamicsmore » of the 14C label as it moved from the surface litter and roots into the mineral soil organic matter pools. ForCent model validation was performed by comparing the observed Enriched Background Isotope Study experimental data with simulated live and dead root biomass ? 14C data, and with soil respiration ? 14C (mineral soil, humus layer, leaf litter layer, and total soil respiration) data. Results show that the model correctly simulates the impact of the Enriched Background Isotope Study 14C experimental treatments on soil respiration ? 14C values for the different soil organic matter pools. Model results suggest that a two-pool root growth model correctly represents root carbon dynamics and inputs to the soil. The model fitting process and sensitivity analysis exposed uncertainty in our estimates of the fraction of mineral soil in the slow and passive pools, dissolved organic carbon flux out of the litter layer into the mineral soil, and mixing of the humus layer into the mineral soil layer.« less

Simultaneous Assay of Isotopic Enrichment and Concentration of Guanidinoacetate and Creatine by Gas Chromatography-Mass Spectrometry

PubMed Central

Kasumov, Takhar; Gruca, Lourdes L.; Dasarathy, Srinivasan; Kalhan, Satish C.

2012-01-01

A gas chromatographic-mass spectrometric (GC-MS) method for the simultaneous measurement of isotopic enrichment and concentration of guanidinoacetic acid and creatine in plasma sample for kinetic studies is reported. The method, based on preparation of the bis(trifluoromethyl)-pyrimidine methyl ester derivatives of guanidinoacetic acid and creatine, is robust and sensitive. The lowest measurable m1 and m3 enrichment for guanidinoacetic acid and creatine, respectively, was 0.3%. The calibration curves for measurements of concentration were linear over a range of 0.5-250 μM guanidinoacetic acid and 2-500 μM for creatine. The method was reliable for inter-assay and intra-assay precision, accuracy and linearity. The technique was applied in a healthy adult to determine in vivo fractional synthesis rate of creatine using primed- constant rate infusion of [1-13C]glycine. It was found that isotopic enrichment of guanidinoacetic acid reached plateau by 30 min of infusion of [1-13C]glycine, indicating either a small pool size or a rapid turnover rate or both, of guanidinoacetic acid. In contrast, tracer appearance in creatin was slow (slope: 0.00097), suggesting a large pool size and a slow rate of synthesis of creatine. This method can be used to estimate rate of synthesis of creatine in-vivo in human and animal studies. PMID:19646413

Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

USGS Publications Warehouse

Ellis, Geoffrey S.; Said-Ahamed, Ward; Lillis, Paul G.; Shawar, Lubna; Amrani, Alon

2017-01-01

Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ34S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ34S values of both BTs and DBTs become progressively heavier, but the difference in the average δ34S value of the BTs and DBTs (Δ34S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34S relative to non-TSR-altered oils, with the BTs being enriched in 34S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ34S BT-DBT values that do not support this interpretation. The δ34S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ34S values observed in the OSCs are enriched in 34S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR, which cannot be determined from other bulk geochemical parameters. Moreover, when combined with additional geochemical and geologic evidence, the sulfur isotopic composition of OSCs in oils can help to identify the source of sulfate for TSR alteration in petroleum reservoirs.

The potential of isotopically enriched magnesium to study bone implant degradation in vivo.

PubMed

Draxler, Johannes; Martinelli, Elisabeth; Weinberg, Annelie M; Zitek, Andreas; Irrgeher, Johanna; Meischel, Martin; Stanzl-Tschegg, Stefanie E; Mingler, Bernhard; Prohaska, Thomas

2017-03-15

This pilot study highlights the substantial potential of using isotopically enriched (non-radioactive) metals to study the fate of biodegradable metal implants. It was possible to show that magnesium (Mg) release can be observed by combining isotopic mass spectrometry and isotopic pattern deconvolution for data reduction, even at low amounts of Mg released a from slowly degrading 26 Mg enriched (>99%) Mg metal. Following implantation into rats, structural in vivo changes were monitored by μCT. Results showed that the applied Mg had an average degradation rate of 16±5μmyear -1 , which corresponds with the degradation rate of pure Mg. Bone and tissue extraction was performed 4, 24, and 52weeks after implantation. Bone cross sections were analyzed by laser ablation inductively coupled plasma mass spectrometry (ICP-MS) to determine the lateral 26 Mg distribution. The 26 Mg/ 24 Mg ratios in digested tissue and excretion samples were analyzed by multi collector ICP-MS. Isotope pattern deconvolution in combination with ICP-MS enabled detection of Mg pin material in amounts as low as 200ppm in bone tissues and 20ppm in tissues up to two fold increased Mg levels with a contribution of pin-derived Mg of up to 75% (4weeks) and 30% (24weeks) were found adjacent to the implant. After complete degradation, no visual bone disturbance or residual pin-Mg could be detected in cortical bone. In organs, increased Δ 26 Mg/ 24 Mg values up to 16‰ were determined compared to control samples. Increased Δ 26 Mg/ 24 Mg values were detected in serum samples at a constant total Mg level. In contrast to urine, feces did not show a shift in the 26 Mg/ 24 Mg ratios. This investigation showed that the organism is capable of handling excess Mg well and that bones fully recover after degradation. Magnesium alloys as bone implants have faced increasing attention over the past years. In vivo degradation and metabolism studies of these implant materials have shown the promising application in orthopaedic trauma surgery. With advance in Mg research it has become increasingly important to monitor the fate of the implant material in the organism. For the first time, the indispensible potential of isotopically enriched materials is documented by applying 26 Mg enriched Mg implants in an animal model. Therefore, the spatial distribution of pin-Mg in bone and the pin-Mg migration and excretion in the organism could be monitored to better understand metal degradation as well as Mg turn over and excretion. Copyright © 2017. Published by Elsevier Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large dataset of δDwax from trees and grasses that aimed to mirror the variability of environmental factors over geological time frames showed the lapse rates were significant, but much smaller than in previous studies. Most importantly our result demonstrated that the lapse rate significantly differed for both transects (p = 0.0068), i.e. 0.87 ± 0.71‰/100 m (R2 = 0.28, p = 0.2841, n = 6) and 2.28 ± 0.82‰/100 m (R2 = 0.34, p = 0.0135, n = 17) for Indian monsoon and Westerly dominated areas, respectively. This suggests that different moisture sources might strongly affected the observed lapse rates. In consequences altitude reconstructions are strongly complicated in areas with likely changing air masses like the Tibetan Plateau.

Stable isotope enrichment in laboratory ant colonies: effects of colony age, metamorphosis, diet, and fat storage

USDA-ARS?s Scientific Manuscript database

Ecologists use stable isotopes to infer diets and trophic levels of animals in food webs, yet some assumptions underlying these inferences have not been thoroughly tested. We used laboratory-reared colonies of Solenopsis invicta Buren (Formicidae: Solenopsidini) to test the effects of metamorphosis,...

RIBBED MUSSEL NITROGEN ISOTOPE SIGNATURES REFLECT NITROGEN SOURCES IN COASTAL MARSHES

EPA Science Inventory

The stable nitrogen isotope ratio in tissue of the ribbed mussel (Geukensia demissa) was investigated as an indicator of the source of nitrogen inputs to coastal salt marshes. Initially, mussels were fed a diet of 15N-enriched algae in the laboratory to determine how the tissue n...

Origin of enormous trace metal enrichments in weathering mantles of Jurassic carbonates: evidence from Sr, Nd and Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.

2013-12-01

Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.

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

USGS Publications Warehouse

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

2009-01-01

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate ??13CVPDB and ??18OVSMOW values are consistent with thermal generation of 13C-depleted and 18O-enriched CO2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13C-enriched carbonate in thermally unaffected coal may be linked to 13C-enrichment in residual CO2 in the process of CO2 reduction via microbial methanogenesis. Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic ??D values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) ??13C and ??15N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen. ?? 2009 Elsevier Ltd. All rights reserved.

The Origin of EM1 Signatures in Basalts From Tristan da Cunha and Gough

NASA Astrophysics Data System (ADS)

Stracke, A.; Willbold, M.; Hemond, C.

2004-12-01

A long-standing hypothesis is that enriched mantle 1 (EM-1)-type ocean island basalt (OIB) sources contain pelagic sediments. Pelagic sediments range in composition from clays to calcareous or siliceous oozes and encompass a wide range of chemical compositions [1]. For geochemical purposes the use of the term pelagic sediments is often restricted to a special group of pelagic sediments with distinctive enrichment of Rare Earth Elements (REE). The geochemical composition of such REE-enriched pelagic sediments, however, is by no means representative of the geochemical composition of pelagic sediments in general. The extremely high REE/non-REE element ratios in REE-enriched pelagic sediments (e.g. high Lu/Hf, Sm/Hf, La/Nb, La/Th, Eu/Ti, and Gd/Ti ratios) translate into high 176Hf/177Hf ratios for given 143Nd/144Nd ratios with time. OIB sources containing this special variety of REE-enriched pelagic sediment should therefore plot above the oceanic basalt array and mixing arrays with these sources are expected to have a shallow slope in a Hf-Nd isotope diagram. Here we present new Hf-Nd isotope and trace element data for EM-1-type OIB from Tristan da Cunha and Gough in the South Atlantic Ocean. The samples from Tristan have a small range in Hf-Nd isotopic composition and plot within the oceanic basalt array in a Hf-Nd isotope diagram. Samples from Gough form a trend with a slope slightly steeper than that of the ocean basalt array in a Hf-Nd isotope diagram. OIB in general have a very restricted range in Gd/Ti and Sm/Hf ratios, and high La/Nb are associated with low Lu/Hf ratios. In detail, samples from Tristan and Gough have the lowest Lu/Hf and highest La/Nb ratios. Thus from the combined Hf-Nd isotope and trace element composition of basalts from Tristan and Gough involvement of this special variety of (REE-enriched) pelagic sediments can be excluded. Similar observations are made, and thus similar arguments hold, for other EM-1-type localities (Walvis ridge [2] and Pitcairn island [3]). Due to the considerable spread in geochemical composition of pelagic or any other group of sediments (e.g. marine sediments with a higher proportion of terrigenous components), it is difficult to attribute characteristic elemental or isotopic signatures to certain groups of sediment. Moreover, subducting sediments are complex mixtures of different types of sediment [1]. Thus it is difficult to find unique evidence either in favor of or against the involvement of sediments in general at Tristan and Gough, or any other individual OIB locality. Also, it appears highly unlikely that sub-arc processing has an equalizing effect on the composition of different subducting sediments [4]. Associating the similar isotopic characteristics of certain OIB groups and/or mantle-end-members (e.g. EM-1) to recycled sediments is therefore also problematic. [1] Plank, T. and C. H. Langmuir, Chem. Geol., 145, 325-394, 1998. [2] Salters, V. J. M. and X. Li, Geochim. Cosmochim. Acta, 68, A554, 2004. [3] Eisele, J., M. Sharma, J. G. Galer, J. Blichert-Toft, C. W. Devey and A. W. Hofmann, Earth Plan. Sci. Lett., 196, 197-212, 2002. [4] Johnson, M. C. and T. Plank, Geochem., Geophys., Geosys., 1, pp. 29, 1999.

Integrated elemental and Sr-Nd-Pb-Hf isotopic studies of Mesozoic mafic dykes from the eastern North China Craton: implications for the dramatic transformation of lithospheric mantle

NASA Astrophysics Data System (ADS)

Liu, Shen; Feng, Caixia; Santosh, M.; Feng, Guangying; Coulson, Ian M.; Xu, Mengjing; Guo, Zhuang; Guo, Xiaolei; Peng, Hao; Feng, Qiang

2018-02-01

Evolution of the lithospheric mantle beneath the North China Craton (NCC) from its Precambrian cratonic architecture until Paleozoic, and the transformation to an oceanic realm during Mesozoic, with implications on the destruction of cratonic root have attracted global attention. Here we present geochemical and isotopic data on a suite of newly identified Mesozoic mafic dyke swarms from the Longwangmiao, Weijiazhuang, Mengjiazhuang, Jiayou, Huangmi, and Xiahonghe areas (Qianhuai Block) along the eastern NCC with an attempt to gain further insights on the lithospheric evolution of the region. The Longwangmiao dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 4.3) and EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.706; ε Nd (t) < -6.3, (206Pb/204Pb) i > 16.6, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.8, ε Hf (t) < -22.4). The Weijiazhuang dykes are sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7), and display similar EM1-like isotopic features ((87Sr/86Sr) i > 0.706; ε Nd (t) < -7.0, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -23.3). The Mengjiazhuang dykes are also sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 2.4) and EM1-like isotopic features((87Sr/86Sr) i > 0.706; ε Nd (t) < -18.4, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). The Jiayou dykes also display sub-alkaline affinity with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7) and EM1-like Sr-Nd-Pb-Hf isotopic features ((87Sr/86Sr) i > 0.706; ε Nd(t) < -15.3, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -18.4). The Huangmi dykes are alkaline (with Na2O + K2O ranging to more than 5.9 wt.%)) with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 9.3) and EM1-like isotopic composition ((87Sr/86Sr) i > 0.705; ε Nd (t) < -15.1, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -12.2). The Xiahonghe dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N = 2.12-2.84) and similar EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.705; ε Nd (t)<-18.0, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). Our data from the various mafic dyke suites suggest that the magmas were derived from EM1-like lithospheric mantle, corresponding to lithospheric mantle modified by the previously foundered lower crust beneath the eastern NCC. Our results suggest contrasting lithospheric evolution from Triassic (212 Ma) to Cretaceous (123 Ma) beneath the NCC. These mafic dykes mark an important phase of lithospheric thinning in the eastern North China Craton.

Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

NASA Astrophysics Data System (ADS)

Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

2017-12-01

The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested for the Canary Island hotspot on the basis of radiogenic isotope characteristics.

Transpiration flow controls Zn transport in Brassica napus and Lolium multiflorum under toxic levels as evidenced from isotopic fractionation

NASA Astrophysics Data System (ADS)

Couder, Eléonore; Mattielli, Nadine; Drouet, Thomas; Smolders, Erik; Delvaux, Bruno; Iserentant, Anne; Meeus, Coralie; Maerschalk, Claude; Opfergelt, Sophie; Houben, David

2015-11-01

Stable zinc (Zn) isotope fractionation between soil and plant has been used to suggest the mechanisms affecting Zn uptake under toxic conditions. Here, changes in Zn isotope composition in soil, soil solution, root and shoot were studied for ryegrass (Lolium multiflorum L.) and rape (Brassica napus L.) grown on three distinct metal-contaminated soils collected near Zn smelters (total Zn 0.7-7.5%, pH 4.8-7.3). The Zn concentrations in plants reflected a toxic Zn supply. The Zn isotopic fingerprint of total soil Zn varied from -0.05‰ to +0.26 ± 0.02‰ (δ66Zn values relative to the JMC 3-0749L standard) among soils, but the soil solution Zn was depleted in 66Zn, with a constant Zn isotope fractionation of about -0.1‰ δ66Zn unit compared to the bulk soil. Roots were enriched with 66Zn relative to soil solution (δ66Znroot - δ66Znsoil solution = Δ66Znroot-soil solution = +0.05 to +0.2 ‰) and shoots were strongly depleted in 66Zn relative to roots (Δ66Znshoot-root = -0.40 to -0.04 ‰). The overall δ66Zn values in shoots reflected that of the bulk soil, but were lowered by 0.1-0.3 ‰ units as compared to the latter. The isotope fractionation between root and shoot exhibited a markedly strong negative correlation (R2 = 0.83) with transpiration per unit of plant weight. Thus, the enrichment with light Zn isotopes in shoot progressed with increasing water flux per unit plant biomass dry weight, showing a passive mode of Zn transport by transpiration. Besides, the light isotope enrichment in shoots compared to roots was larger for rape than for rye grass, which may be related to the higher Zn retention in rape roots. This in turn may be related to the higher cation exchange capacity of rape roots. Our finding can be of use to trace the biogeochemical cycles of Zn and evidence the tolerance strategies developed by plants in Zn-excess conditions.

Mercury isotope fractionation during ore retorting in the Almadén mining district, Spain

USGS Publications Warehouse

Gray, John E.; Pribil, Michael J.; Higueras, Pablo L.

2013-01-01

Almadén, Spain, is the world's largest mercury (Hg) mining district, which has produced over 250,000 metric tons of Hg representing about 30% of the historical Hg produced worldwide. The objective of this study was to measure Hg isotopic compositions of cinnabar ore, mine waste calcine (retorted ore), elemental Hg (Hg0(L)), and elemental Hg gas (Hg0(g)), to evaluate potential Hg isotopic fractionation. Almadén cinnabar ore δ202Hg varied from − 0.92 to 0.15‰ (mean of − 0.56‰, σ = 0.35‰, n = 7), whereas calcine was isotopically heavier and δ202Hg ranged from − 0.03‰ to 1.01‰ (mean of 0.43‰, σ = 0.44‰, n = 8). The average δ202Hg enrichment of 0.99‰ between cinnabar ore and calcines generated during ore retorting indicated Hg isotopic mass dependent fractionation (MDF). Mass independent fractionation (MIF) was not observed in any of the samples in this study. Laboratory retorting experiments of cinnabar also were carried out to evaluate Hg isotopic fractionation of products generated during retorting such as calcine, Hg0(L), and Hg0(g). Calcine and Hg0(L) generated during these retorting experiments showed an enrichment in δ202Hg of as much as 1.90‰ and 0.67‰, respectively, compared to the original cinnabar ore. The δ202Hg for Hg0(g) generated during the retorting experiments was as much as 1.16‰ isotopically lighter compared to cinnabar, thus, when cinnabar ore was roasted, the resultant calcines formed were isotopically heavier, whereas the Hg0(g) generated was isotopically lighter in Hg isotopes.

Testing the chondrule-rich accretion model for planetary embryos using calcium isotopes

NASA Astrophysics Data System (ADS)

Amsellem, Elsa; Moynier, Frédéric; Pringle, Emily A.; Bouvier, Audrey; Chen, Heng; Day, James M. D.

2017-07-01

Understanding the composition of raw materials that formed the Earth is a crucial step towards understanding the formation of terrestrial planets and their bulk composition. Calcium is the fifth most abundant element in terrestrial planets and, therefore, is a key element with which to trace planetary composition. However, in order to use Ca isotopes as a tracer of Earth's accretion history, it is first necessary to understand the isotopic behavior of Ca during the earliest stages of planetary formation. Chondrites are some of the oldest materials of the Solar System, and the study of their isotopic composition enables understanding of how and in what conditions the Solar System formed. Here we present Ca isotope data for a suite of bulk chondrites as well as Allende (CV) chondrules. We show that most groups of carbonaceous chondrites (CV, CI, CR and CM) are significantly enriched in the lighter Ca isotopes (δ 44 / 40 Ca = + 0.1 to + 0.93 ‰) compared with bulk silicate Earth (δ 44 / 40 Ca = + 1.05 ± 0.04 ‰, Huang et al., 2010) or Mars, while enstatite chondrites are indistinguishable from Earth in Ca isotope composition (δ 44 / 40 Ca = + 0.91 to + 1.06 ‰). Chondrules from Allende are enriched in the heavier isotopes of Ca compared to the bulk and the matrix of the meteorite (δ 44 / 40 Ca = + 1.00 to + 1.21 ‰). This implies that Earth and Mars have Ca isotope compositions that are distinct from most carbonaceous chondrites but that may be like chondrules. This Ca isotopic similarity between Earth, Mars, and chondrules is permissive of recent dynamical models of planetary formation that propose a chondrule-rich accretion model for planetary embryos.

Laser ion source for isobaric heavy ion collider experiment.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is (96)Ru + (96)Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

Calcium and Titanium Isotope Fractionation in CAIS: Tracers of Condensation and Inheritance in the Early Solar Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Simon, J. I.; Jordan, M. K.; Tappa, M. J.; Kohl, I. E.; Young, E. D.

2016-01-01

The chemical and isotopic compositions of calcium-aluminum-rich inclusions (CAIs) can be used to understand the conditions present in the protoplantary disk where they formed. The isotopic compositions of these early-formed nebular materials are largely controlled by chemical volatility. The isotopic effects of evaporation/sublimation, which are well explained by both theory and experimental work, lead to enrichments of the heavy isotopes that are often exhibited by the moderately refractory elements Mg and Si. Less well understood are the isotopic effects of condensation, which limits our ability to determine whether a CAI is a primary condensate and/or retains any evidence of its primordial formation history.

Reactors are indispensable for radioisotope production.

PubMed

Mushtaq, Ahmad

2010-12-01

Radioisotopes can be produced by reactors and accelerators. For certain isotopes there could be an advantage to a certain production method. However, nowadays many reports suggest, that useful isotopes needed in medicine, industry and research could be produced efficiently and dependence on reactors using enriched U-235 may be eliminated. In my view reactors and accelerators will continue to play their role side by side in the supply of suitable and economical sources of isotopes.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

An experimental investigation of fractionation by sputter deposition. [application to solar wind irradiation of lunar soil

NASA Technical Reports Server (NTRS)

Paruso, D. M.; Cassidy, W. A.; Hapke, B. W.

1978-01-01

Artificial glass targets composed of elements varying widely in atomic weight were irradiated at an angle of incidence of 45 deg by 2-keV hydrogen ions at a current density of .33 mA/sq cm, and sputtered atoms were caught on a molybdenum film. Analyses of the sputter-deposited films and unsputtered target glasses were carried out by electron microprobe. The backward-sputtered component was found to be enriched in elements of low atomic weight, while the forward-sputtered component was enriched in heavy atoms. These results indicate that at the lunar surface lighter elements and isotopes would tend to be ejected in backward directions, escaping directly through the openings which admit bombarding ions without first striking an adjacent grain surface; heavy elements and isotopes would be forward-sputtered deeper into the soil and be preferentially retained, contributing to the reported enrichments of heavy elements and isotopes. Additional results show that the binding energy of an element in its oxide form influences the sticking coefficient of a sputtered atom; elements of low binding energy are likely to desorb, while elements of high binding energy tend to stick to the first bounce surface.

$sup 18$O enrichment process in UO$sub 2$F$sub 2$ utilizing laser light

DOEpatents

DePoorter, G.L.; Rofer-DePoorter, C.K.

1975-12-01

Photochemical reaction induced by laser light is employed to separate oxygen isotopes. A solution containing UO$sub 2$F$sub 2$, HF, H$sub 2$O and a large excess of CH$sub 3$OH is irradiated with laser light of appropriate wavelength to differentially excite the UO$sub 2$$sup 2+$ ions containing $sup 16$O atoms and cause a reaction to proceed in accordance with the reaction 2 UO$sub 2$F$sub 2$ + CH$sub 3$OH + 4 HF $Yields$ 2 UF$sub 4$ down arrow + HCOOH + 3 H$sub 2$O. Irradiation is discontinued when about 10 percent of the UO$sub 2$F$sub 2$ has reacted, the UF$sub 4$ is filtered from the reaction mixture and the residual CH$sub 3$OH and HF plus the product HCOOH and H$sub 2$O are distilled away from the UO$sub 2$F$sub 2$ which is thereby enriched in the $sup 18$O isotope, or the solution containing the UO$sub 2$F$sub 2$ may be photochemically processed again to provide further enrichment in the $sup 18$O isotope.

Fractionation of Nitrogen Isotopes by Plants with Different Types of Mycorrhiza in Mountain Tundra Ecosystems

NASA Astrophysics Data System (ADS)

Buzin, Igor; Makarov, Mikhail; Maslov, Mikhail; Tiunov, Alexei

2017-04-01

We studied nitrogen concentration and nitrogen isotope composition in plants from four mountain tundra ecosystems in the Khibiny Mountains. The ecosystems consisted of a toposequence beginning with the shrub-lichen heath (SLH) on the ridge and upper slope, followed by the Betula nana dominated shrub heath (SH) on the middle slope, the cereal meadow (CM) on the lower slope and the sedge meadow (SM) at the bottom of the slope. The inorganic nitrogen concentration of the soils from the studied ecosystems were significantly different; the SLH soil was found to contain the minimum concentration of N-NH4+ and N-NO3- , while in the soils of the meadow ecosystems these concentrations were much higher. The concentration of nitrogen in leaves of the dominant plant species in all of the ecosystems is directly connected with the concentration of inorganic nitrogen in the soils, regardless of the plant's mycorrhizal symbiosis type. However, such a correlation is not apparent in the case of plant roots, especially for plant roots with ectomycorrhiza and ericoid mycorrhiza. The majority of plant species with these types of mycorrhiza in the SH and particularly in the CM were enriched in 15N in comparison with the SLH (such plants were not found within the SM). This could be due to several reasons: 1) the decreasing role of mycorrhiza in nitrogen consumption and therefore in the fractionation of isotopes in the relatively-N-enriched ecosystems; 2) the use of relatively-15N-enriched forms of nitrogen for plant nutrition in meadow ecosystems. This heavier nitrogen isotope composition in plant roots with ectomycorrhiza and ericoid mycorrhiza in ecosystems with available nitrogen enriched soils doesn't correspond to the classical idea of mycorrhiza decreasing participation in nitrogen plant nutrition. The analysis of the isotope composition of separate labile forms of nitrogen makes it possible to explain the phenomenon. Not all arbuscular mycorrhizal species within the sedge meadow were 15N-enriched in comparison with other ecosystems. This could either be explained by the different role of mycorrhiza in nitrogen plant nutrition of different arbuscular mycorrhizal plant species or by the primary usage of various nitrogen compounds with different levels of 15N concentration in individual plant species. Acknowledgement: This study was supported by the Russian Foundation for Basic Research (16-04-00544).

Validation of a single biopsy approach and bolus protein feeding to determine myofibrillar protein synthesis in stable isotope tracer studies in humans

PubMed Central

2011-01-01

Background Minimizing the number of muscle biopsies has important methodological implications and minimizes subject discomfort during a stable isotope amino acid infusion. We aimed to determine the reliability of obtaining a single muscle biopsy for the calculation of muscle protein fractional synthetic rate (FSR) as well as the amount of incorporation time necessary to obtain that biopsy after initiating a stable isotope infusion (Study 1). The calculation of muscle protein FSR requires tracer steady-state during the stable isotope infusion. Therefore, a second aim was to examine if steady-state conditions are compromised in the precursor pools (plasma free or muscle intracellular [IC]) after ingestion of a tracer enriched protein drink and after resistance exercise (Study 2). Methods Sixteen men (23 ± 3 years; BMI = 23.8 ± 2.2 kg/m2, means ± SD) were randomized to perform Study 1 or Study 2 (n = 8, per study). Subjects received a primed, constant infusion of L-[ring-13C6]phenylalanine coupled with muscle biopsies of the vastus lateralis to measure rates of myofibrillar protein synthesis (MPS). Subjects in Study 2 were fed 25 g of whey protein immediately after an acute bout of unilateral resistance exercise. Results There was no difference (P = 0.3) in rates of MPS determined using the steady-state precursor-product equation and determination of tracer incorporation between sequential biopsies 150 min apart or using plasma protein as the baseline enrichment, provided the infusion length was sufficient (230 ± 0.3 min). We also found that adding a modest amount of tracer (4% enriched), calculated based on the measured phenylalanine content of the protein (3.5%) in the drink, did not compromise steady-state conditions (slope of the enrichment curve not different from zero) in the plasma free or, more importantly, the IC pool (both P > 0.05). Conclusions These data demonstrate that the single biopsy approach yields comparable rates of muscle protein synthesis, provided a longer incorporation time is utilized, to that seen with a traditional two biopsy approach. In addition, we demonstrate that enriching protein-containing drinks with tracer does not disturb isotopic steady-state and thus both are reliable techniques to determine rates of MPS in humans. PMID:21388545

Isospin degree of freedom in even-even 68-76Ge and 62-70Zn isotopes

NASA Astrophysics Data System (ADS)

Jalili Majarshin, A.

2018-01-01

The introduction of isotopic spin is significant in light nuclei as Ge and Zn isotopes in order to take into account isospin effects on energy spectra. Dynamical symmetries in spherical, γ-soft limits and transition in the interacting boson model IBM-3 are analyzed. Analytic expressions and exact eigenenergies, electromagnetic transitions probabilities are obtained for the transition between spherical and γ-soft shapes by using the Bethe ansatz within an infinite-dimensional Lie algebra in light mass nuclei. The corresponding algebraic structure and reduction chain are studied in IBM-3. For examples, the nuclear structure of the 68-76Ge and 62-70Zn isotopes is calculated in IBM-3 and compared with experimental results.

Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Gibson, Everett K., Jr.; Golden, D. C.; Ming, Douglas W.; McKay, Gordon A.

2003-01-01

An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

Formation of medical radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu in photonuclear reactions

NASA Astrophysics Data System (ADS)

Danagulyan, A. S.; Hovhannisyan, G. H.; Bakhshiyan, T. M.; Avagyan, R. H.; Avetisyan, A. E.; Kerobyan, I. A.; Dallakyan, R. K.

2015-06-01

The possibility of the photonuclear production of radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu is discussed. Reaction yields were measured by the gamma-activation method. The enriched tin isotopes 112, 118Sn and Te and HfO2 of natural isotopic composition were used as targets. The targets were irradiated at the linear electron accelerator of Alikhanian National Science Laboratory (Yerevan) at the energy of 40 MeV. The experimental results obtained in this way reveal that the yield and purity of radioisotopes 111In and 117 mSn are acceptable for their production via photonuclear reactions. Reactions proceeding on targets from Te and HfO2 of natural isotopic composition and leading to the formation of 124Sb and 177Lu have small yields and are hardly appropriate for the photoproduction of these radioisotopes even in the case of enriched targets.

An IBM-3 analysis of the nuclei just beyond the magic numbers N = Z = 28

NASA Astrophysics Data System (ADS)

Elliott, J. P.; Evans, J. A.; Lac, V. S.; Long, G. L.

1996-02-01

The isospin-invariant form IBM-3 of the interacting boson model has been used to study energies and electromagnetic properties of the isotopes of nickel, zinc, germanium and selenium in the first half of the 1p {3}/{2}, 0f {5}/{2} and 1p {1}/{2} shell. The hamiltonian and electromagnetic operators vary with boson number and isospin in a manner determined by a mapping into the shell-model based on seniority and reduced isospin.

Main features of detectors and isotopes to investigate double beta decay with increased sensitivity

NASA Astrophysics Data System (ADS)

Barabash, A. S.

2018-03-01

The current situation in double beta decay experiments, the characteristics of modern detectors and the possibility of increasing the sensitivity to neutrino mass in future experiments are discussed. The issue of the production and use of enriched isotopes in double beta decay experiments is discussed in addition.

COMPARISON OF STABLE-NITROGEN (15N/14N) ISOTOPE RATIOS IN LARGE MOUTH BASS SCALES AND MUSCLE TISSUE

EPA Science Inventory

Stable-nitrogen (15N/14N) isotope ratios of fish tissue are currently used to determine trophic structure, contaminant bioaccumulation, and the level of anthropogenic nitrogen enrichment in aquatic systems. The most common tissue used for these measurements is fileted dorsal musc...

Bioaccumulation and enantiomeric profiling of organochlorine pesticides and persistent organic pollutants in the killer whale (Orcinus orca) from British and Irish waters.

PubMed

McHugh, Brendan; Law, Robin J; Allchin, Colin R; Rogan, Emer; Murphy, Sinead; Foley, M Barry; Glynn, Denise; McGovern, Evin

2007-11-01

Concentrations and enantiomeric profiles for a range of organochlorine compounds are reported in blubber samples from a number of individual killer whales (Orcinus orca) from British and Irish waters. Elevated contaminant levels and enriched isotopic ratios were determined in one individual whale sampled in the Scottish Western Isles compared to the others suggesting marine mammal based dietary influences. The potential application of isotopic ratios to model contaminant uptake, enantioselective enrichment and accumulation is demonstrated. Data are presented which provide information on enantioselective enrichment factors (EFs) for o,p'-DDT, alpha-HCH and toxaphene congeners CHB26 and CHB 50. This dataset further improves the current database on reported levels of a number of contaminants and provides additional background information on potential metabolic processes in killer whales from British and Irish waters.

Neutron capture cross sections of Kr

NASA Astrophysics Data System (ADS)

Fiebiger, Stefan; Baramsai, Bayarbadrakh; Couture, Aaron; Krtička, Milan; Mosby, Shea; Reifarth, René; O'Donnell, John; Rusev, Gencho; Ullmann, John; Weigand, Mario; Wolf, Clemens

2018-01-01

Neutron capture and β- -decay are competing branches of the s-process nucleosynthesis path at 85Kr [1], which makes it an important branching point. The knowledge of its neutron capture cross section is therefore essential to constrain stellar models of nucleosynthesis. Despite its importance for different fields, no direct measurement of the cross section of 85Kr in the keV-regime has been performed. The currently reported uncertainties are still in the order of 50% [2, 3]. Neutron capture cross section measurements on a 4% enriched 85Kr gas enclosed in a stainless steel cylinder were performed at Los Alamos National Laboratory (LANL) using the Detector for Advanced Neutron Capture Experiments (DANCE). 85Kr is radioactive isotope with a half life of 10.8 years. As this was a low-enrichment sample, the main contaminants, the stable krypton isotopes 83Kr and 86Kr, were also investigated. The material was highly enriched and contained in pressurized stainless steel spheres.

Sedimentary evidence for enhanced hydrological cycling in response to rapid carbon release during the early Toarcian oceanic anoxic event

NASA Astrophysics Data System (ADS)

Izumi, Kentaro; Kemp, David B.; Itamiya, Shoma; Inui, Mutsuko

2018-01-01

A pronounced excursion in the carbon-isotope composition of biospheric carbon and coeval seawater warming during the early Toarcian (∼183 Ma) has been linked to the large-scale transfer of 12C-enriched carbon to the oceans and atmosphere. A European bias in the distribution of available data means that the precise pattern, tempo and global expression of this carbon cycle perturbation, and the associated environmental responses, remain uncertain. Here, we present a new cm-scale terrestrial-dominated carbon-isotope record through an expanded lower Toarcian section from Japan that displays a negative excursion pattern similar to marine and terrestrial carbon-isotope records documented from Europe. These new data suggest that 12C-enriched carbon was added to the biosphere in at least one rapid, millennial-scale pulse. Sedimentological analysis indicates a close association between the carbon-isotope excursion and high-energy sediment transport and enhanced fluvial discharge. Together, these data support the hypothesis that a sudden strengthening of the global hydrological cycle occurred in direct and immediate response to rapid carbon release and atmospheric warming.

Stable carbon isotope fractionation of trans-1,2-dichloroethylene during co-metabolic degradation by methanotrophic bacteria

USGS Publications Warehouse

Brungard, Karen L.; Munakata-Marr, Junko; Johnson, Craig A.; Mandernack, Kevin W.

2003-01-01

Changes in the carbon isotope ratio (δ13C) of trans-1,2-dichloroethylene (t-DCE) were measured during its co-metabolic degradation by Methylomonas methanica, a type I methanotroph, and Methylosinus trichosporium OB3b, a type II methanotroph. In closed-vessel incubation experiments with each bacterium, the residual t-DCE became progressively enriched in 13C, indicating isotopic fractionation. From these experiments, the biological fractionation during t-DCE co-metabolism, expressed as ε, was measured to be -3.50/00 for the type I culture and -6.70/00 for the type II culture. This fractionation effect and subsequent enrichment in the δ13C of the residual t-DCE can thus be applied to determine the extent of biodegradation of DCE by these organisms. Based on these results, isotopic fractionation clearly warrants further study, as measured changes in the δ13C values of chlorinated solvents could ultimately be used to monitor the extent of biodegradation in laboratory or field settings where co-metabolism by methanotrophs occurs.

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

PubMed

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

2017-08-01

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

Electromagnetic Radiation Disturbed the Photosynthesis of Microcystis aeruginosa at the Proteomics Level.

PubMed

Tang, Chao; Yang, Chuanjun; Yu, Hui; Tian, Shen; Huang, Xiaomei; Wang, Weiyi; Cai, Peng

2018-01-11

Photosynthesis of Microcystis aeruginosa under Electromagnetic Radiation (1.8 GHz, 40 V/m) was studied by using the proteomics. A total of 30 differentially expressed proteins, including 15 up-regulated and 15 down-regulated proteins, were obtained in this study. The differentially expressed proteins were significantly enriched in the photosynthesis pathway, in which the protein expression levels of photosystems II cytochrome b559 α subunit, cytochrome C550, PsbY, and F-type ATP synthase (a, b) decreased. Our results indicated that electromagnetic radiation altered the photosynthesis-related protein expression levels, and aimed at the function of photosynthetic pigments, photosystems II potential activity, photosynthetic electron transport process, and photosynthetic phosphorylation process of M. aeruginosa. Based on the above evidence, that photoreaction system may be deduced as a target of electromagnetic radiation on the photosynthesis in cyanobacteria; the photoreaction system of cyanobacteria is a hypothetical "shared target effector" that responds to light and electromagnetic radiation; moreover, electromagnetic radiation does not act on the functional proteins themselves but their expression processes.

Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

NASA Technical Reports Server (NTRS)

Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

2004-01-01

Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

The Origin and Evolution of Nucleosynthetic Sr Isotope Variability in Calcium and Aluminum-rich Refractory Inclusions

NASA Astrophysics Data System (ADS)

Myojo, Kunihiro; Yokoyama, Tetsuya; Okabayashi, Satoki; Wakaki, Shigeyuki; Sugiura, Naoji; Iwamori, Hikaru

2018-01-01

Nucleosynthetic isotope anomalies in meteorites are useful for investigating the origin of materials in the protoplanetary disk and dynamical processes of planetary formation. In particular, calcium and aluminum-rich inclusions (CAIs) found in chondrites are key minerals for decoding the initial conditions of the solar system before the accretion of small planetary bodies. In this study, we report isotopic analyses for three Allende CAIs, fluffy type A (FTA), type B, and fine-grained spinel rich (FS) inclusions, with a specific emphasis on the measurements of 84Sr/86Sr ratios. It was found that the average μ 84Sr values (106 relative deviations from a standard material) were 175, 129, and 56 ppm for the samples of FTA, type B, and FS inclusions, respectively. Additionally, the FTA samples exhibited heterogeneous μ 84Sr values, while those for the type B and FS inclusions were homogeneous within individual inclusions. The elevated μ 84Sr values were most likely explained by the relative enrichment of r-process nuclides in the CAI formation region. The variation of μ 84Sr values between the FTA and type B inclusions, as well as within the FTA inclusion, suggests the presence of multiple CAI source reservoirs with distinct isotopic compositions, which is either inherited from isotopic heterogeneity in the molecular cloud or caused by the selective destruction of r-process-enriched supernova grains via nebular thermal processing. On the other hand, the reaction between a refractory precursor of the FS inclusion and a gaseous reservoir enriched in Mg, Si, and 16O resulted in the lowest μ 84Sr values for the FS inclusion.

Ratios of Carbon Isotopes in Microbial Lipids as an Indicator of Substrate Usage

PubMed Central

Abraham, Wolf-Rainer; Hesse, Christian; Pelz, Oliver

1998-01-01

The occurrence and abundance of microbial fatty acids have been used for the identification of microorganisms in microbial communities. However, these fatty acids can also be used as indicators of substrate usage. For this, a systematic investigation of the discrimination of the stable carbon isotopes by different microorganisms is necessary. We grew 11 strains representing major bacterial and fungal species with four different isotopically defined carbon sources and determined the isotope ratios of fatty acids of different lipid fractions. A comparison of the differences of δ13C values of palmitic acid (C16:0) with the δ13C values of the substrates revealed that the isotope ratio is independent of the growth stage and that most microorganisms showed enrichment of C16:0 with 13C when growing on glycerol. With the exception of Burkholderia gladioli, all microorganism showed depletion of 13C in C16:0 while incorporating the carbons of glucose, and most of them were enriched with 13C from mannose, with the exception of Pseudomonas fluorescens and the Zygomycotina. Usually, the glycolipid fractions are depleted in 13C compared to the phospholipid fractions. The δ13C pattern was not uniform within the different fatty acids of a given microbial species. Generally, tetradecanoic acid (C14:0) was depleted of 13C compared to palmitic acid (C16:0) while octadecanoic acid (C18:0) was enriched. These results are important for the calibration of a new method in which δ13C values of fatty acids from the environment delineate the use of bacterial substrates in an ecosystem. PMID:9797266

Improved sample preparation of glyphosate and methylphosphonic acid by EPA method 6800A and time-of-flight mass spectrometry using novel solid-phase extraction.

PubMed

Wagner, Rebecca; Wetzel, Stephanie J; Kern, John; Kingston, H M Skip

2012-02-01

The employment of chemical weapons by rogue states and/or terrorist organizations is an ongoing concern in the United States. The quantitative analysis of nerve agents must be rapid and reliable for use in the private and public sectors. Current methods describe a tedious and time-consuming derivatization for gas chromatography-mass spectrometry and liquid chromatography in tandem with mass spectrometry. Two solid-phase extraction (SPE) techniques for the analysis of glyphosate and methylphosphonic acid are described with the utilization of isotopically enriched analytes for quantitation via atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry (APCI-Q-TOF-MS) that does not require derivatization. Solid-phase extraction-isotope dilution mass spectrometry (SPE-IDMS) involves pre-equilibration of a naturally occurring sample with an isotopically enriched standard. The second extraction method, i-Spike, involves loading an isotopically enriched standard onto the SPE column before the naturally occurring sample. The sample and the spike are then co-eluted from the column enabling precise and accurate quantitation via IDMS. The SPE methods in conjunction with IDMS eliminate concerns of incomplete elution, matrix and sorbent effects, and MS drift. For accurate quantitation with IDMS, the isotopic contribution of all atoms in the target molecule must be statistically taken into account. This paper describes two newly developed sample preparation techniques for the analysis of nerve agent surrogates in drinking water as well as statistical probability analysis for proper molecular IDMS. The methods described in this paper demonstrate accurate molecular IDMS using APCI-Q-TOF-MS with limits of quantitation as low as 0.400 mg/kg for glyphosate and 0.031 mg/kg for methylphosphonic acid. Copyright © 2012 John Wiley & Sons, Ltd.

Diel variations in carbon isotopic composition and concentration of organic acids and their impact on plant dark respiration in different species.

PubMed

Lehmann, M M; Wegener, F; Werner, R A; Werner, C

2016-09-01

Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 . © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

Inside HOLMES experiment: 163Ho metallic target production for the micro-calorimeter absorber

NASA Astrophysics Data System (ADS)

Pizzigoni, G.; Alpert, B.; Balata, M.; Bennett, D.; Biasotti, M.; Boragno, C.; Brofferio, C.; De Gerone, M.; Dressler, R.; Faverazani, M.; Ferri, E.; Folwer, J.; Gatti, F.; Giachero, A.; Heinitz, S.; Hilton, G.; Köster, U.; Lusignoli, M.; Maino, M.; Mates, J.; Nisi, S.; Nizzolo, R.; Nucciotti, A.; Pessina, G.; Puiu, A.; Ragazzi, S.; Reintsema, C.; Ribeiro Gomes, M.; Shmidt, D.; Schumann, D.; Sisti, M.; Swetz, D.; Terranova, F.; Ullom, J.; Day, P. K.

2016-07-01

The main goal in the HOLMES experiment is the neutrino mass measurement using an array of 1000 micro-calorimeters with standard metallic absorber. A good isotope for such measurement is the 163Ho, those isotopes embedded in the metallic absorber will be 1011-1013. Since 163Ho is not available in nature, a dedicated process must be set up to produce the amount needed for this neutrino mass experiment. The process with the highest born-up cross-section is the neutron irradiation of Er2O3 enriched in 162Er: 162Er(n,γ)163Er →163Ho+νe, where the decay is an EC with half-life of about 75 min and the (n,γ) is about 20 barns for thermal neutron. After the neutron irradiation in the oxide powder there are several radioactive isotopes which are potentially disturbing because of the background that they cause below 5 keV. The chemical separation of holmium from the irradiation enriched Er2O3 powder is therefore mandatory and will be performed by means of ion exchange chromatography. On the end of those processes the oxide powder enriched in 162Er will have the 163Ho isotope number required. The holmium chemical state influences the end point of the EC spectrum, in order to avoid such effect it is necessary to embed in the absorber only the metallic isotope. Reduction and distillation technique allowed us to obtain a pure metallic holmium, starting from natural oxide holmium. This technique will be applied on the irradiated oxide powder to obtain the metallic 163Ho, ready to be embedded in the micro-calorimeter absorber.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Multiple isotope analyses of the pike tapeworm Triaenophorus nodulosus reveal peculiarities in consumer-diet discrimination patterns.

PubMed

Behrmann-Godel, J; Yohannes, E

2015-03-01

Previous studies of dietary isotope discrimination have led to the general expectation that a consumer will exhibit enriched stable isotope levels relative to its diet. Parasite-host systems are specific consumer-diet pairs in which the consumer (parasite) feeds exclusively on one dietary source: host tissue. However, the small numbers of studies previously carried out on isotopic discrimination in parasite-host (ΔXP-HT) systems have yielded controversial results, showing some parasites to be isotopically depleted relative to their food source, while others are enriched or in equilibrium with their hosts. Although the mechanism for these deviations from expectations remains to be understood, possible influences of specific feeding niche or selection for only a few nutritional components by the parasite are discussed. ΔXP-HT for multiple isotopes (δ13C, δ15N, δ34S) were measured in the pike tapeworm Triaenophorus nodulosus and two of its life-cycle fish hosts, perch Perca fluviatilis and pike Esox lucius, within which T. nodulosus occupies different feeding locations. Variability in the value of ΔXP-HT calculated for the parasite and its different hosts indicates an influence of feeding location on isotopic discrimination. In perch liver ΔXP-HT was relatively more negative for all three stable isotopes. In pike gut ΔXP-HT was more positive for δ13C, as expected in conventional consumer-diet systems. For parasites feeding on pike gut, however, the δ15N and δ34S isotope values were comparable with those of the host. We discuss potential causes of these deviations from expectations, including the effect of specific parasite feeding niches, and conclude that ΔXP-HT should be critically evaluated for trophic interactions between parasite and host before general patterns are assumed.

Nickel and zinc isotope fractionation in hyperaccumulating and nonaccumulating plants.

PubMed

Deng, Teng-Hao-Bo; Cloquet, Christophe; Tang, Ye-Tao; Sterckeman, Thibault; Echevarria, Guillaume; Estrade, Nicolas; Morel, Jean-Louis; Qiu, Rong-Liang

2014-10-21

Until now, there has been little data on the isotope fractionation of nickel (Ni) in higher plants and how this can be affected by plant Ni and zinc (Zn) homeostasis. A hydroponic cultivation was conducted to investigate the isotope fractionation of Ni and Zn during plant uptake and translocation processes. The nonaccumulator Thlaspi arvense, the Ni hyperaccumulator Alyssum murale and the Ni and Zn hyperaccumulator Noccaea caerulescens were grown in low (2 μM) and high (50 μM) Ni and Zn solutions. Results showed that plants were inclined to absorb light Ni isotopes, presumably due to the functioning of low-affinity transport systems across root cell membrane. The Ni isotope fractionation between plant and solution was greater in the hyperaccumulators grown in low Zn treatments (Δ(60)Ni(plant-solution) = -0.90 to -0.63‰) than that in the nonaccumulator T. arvense (Δ(60)Ni(plant-solution) = -0.21‰), thus indicating a greater permeability of the low-affinity transport system in hyperaccumulators. Light isotope enrichment of Zn was observed in most of the plants (Δ(66)Zn(plant-solution) = -0.23 to -0.10‰), but to a lesser extent than for Ni. The rapid uptake of Zn on the root surfaces caused concentration gradients, which induced ion diffusion in the rhizosphere and could result in light Zn isotope enrichment in the hyperaccumulator N. caerulescens. In high Zn treatment, Zn could compete with Ni during the uptake process, which reduced Ni concentration in plants and decreased the extent of Ni isotope fractionation (Δ(60)Ni(plant-solution) = -0.11 to -0.07‰), indicating that plants might take up Ni through a low-affinity transport system of Zn. We propose that isotope composition analysis for transition elements could become an empirical tool to study plant physiological processes.

Stable-isotope analysis of a deep-sea benthic-fish assemblage: evidence of an enriched benthic food web.

PubMed

Boyle, M D; Ebert, D A; Cailliet, G M

2012-04-01

In this study, fishes and invertebrates collected from the continental slope (1000 m) of the eastern North Pacific Ocean were analysed using stable-isotope analysis (SIA). Resulting trophic positions (T(P) ) were compared to known diets and habitats from the literature. Dual isotope plots indicated that most species groups (invertebrates and fishes) sorted as expected along the carbon and nitrogen axes, with less intraspecific variability than interspecific variability. Results also indicated an isotopically distinct benthic and pelagic food web, as the benthic food web was more enriched in both nitrogen and carbon isotopes. Trophic positions from SIA supported this finding, resulting in the assignment of fishes to different trophic positions from those expected based on published dietary information. These differences can be explained largely by the habitat of the prey and the percentage of the diet that was scavenged. A mixing model estimated dietary contributions of prey similar to those of the known diet of Bathyraja trachura from stomach-content analysis (SCA). Linear regressions indicated that trophic positions calculated from SIA and SCA, when plotted against B. trachura total length for 32 individuals, exhibited similar variation and patterns. Only the T(P) from SCA yielded significant results (stomach content: P < 0·05, stable isotope: P > 0·05). © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.

Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

PubMed

Goevert, Dennis; Conrad, Ralf

2008-11-01

Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

OpenMebius: an open source software for isotopically nonstationary 13C-based metabolic flux analysis.

PubMed

Kajihata, Shuichi; Furusawa, Chikara; Matsuda, Fumio; Shimizu, Hiroshi

2014-01-01

The in vivo measurement of metabolic flux by (13)C-based metabolic flux analysis ((13)C-MFA) provides valuable information regarding cell physiology. Bioinformatics tools have been developed to estimate metabolic flux distributions from the results of tracer isotopic labeling experiments using a (13)C-labeled carbon source. Metabolic flux is determined by nonlinear fitting of a metabolic model to the isotopic labeling enrichment of intracellular metabolites measured by mass spectrometry. Whereas (13)C-MFA is conventionally performed under isotopically constant conditions, isotopically nonstationary (13)C metabolic flux analysis (INST-(13)C-MFA) has recently been developed for flux analysis of cells with photosynthetic activity and cells at a quasi-steady metabolic state (e.g., primary cells or microorganisms under stationary phase). Here, the development of a novel open source software for INST-(13)C-MFA on the Windows platform is reported. OpenMebius (Open source software for Metabolic flux analysis) provides the function of autogenerating metabolic models for simulating isotopic labeling enrichment from a user-defined configuration worksheet. Analysis using simulated data demonstrated the applicability of OpenMebius for INST-(13)C-MFA. Confidence intervals determined by INST-(13)C-MFA were less than those determined by conventional methods, indicating the potential of INST-(13)C-MFA for precise metabolic flux analysis. OpenMebius is the open source software for the general application of INST-(13)C-MFA.

Application of a Boson Expansion formalism based on the Random Phase Approximation to samarium isotopes

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

Jamaluddin, M.B.

1986-01-01

The Boson Expansion Theory of Kishimoto and Tamura has proved to be very successful in describing quadrupole collective motions in even-even nuclei. This theory, however, involves a complicated transformation from the Tamm-Dancoff phonons to the phonons of the random Phase Approximation. In this thesis a Boson Expansion formalism, derived directly from the Random Phase Approximation and set forth by Pedracchi and Tamura, is used to derive the boson forms of the nuclear Hamiltonian and the electromagnetic transition operator. Detailed discussions of the formalism of Pedrocchi and Tamura and its extension needed to perform realistic calculations are presented. The technique usedmore » to deriving the boson forms and the formulae used in the calculations are also given a thorough treatment to demonstrate the simplicity of this approach. Finally, the theory is tested by applying it to calculate the energy levels and some electromagnetic properties of the Samarium isotopes. The results show that the present theory is capable of describing the range of behavior from a vibrational to a rotational character of the Samarium isotopes as well as the previous theory.« less

Effects of glacial meltwater inflows and moat freezing on mixing in an ice-covered antarctic lake as interpreted from stable isotope and tritium distributions

USGS Publications Warehouse

Miller, L.G.; Aiken, G.R.

1996-01-01

Perennially ice-covered lakes in the McMurdo Dry Valleys have risen several meters over the past two decades due to climatic warming and increased glacial meltwater inflow. To elucidate the hydrologic responses to changing climate and the effects on lake mixing processes we measured the stable isotope (??18O and ??D) and tritium concentrations of water and ice samples collected in the Lake Fryxell watershed from 1987 through 1990. Stable isotope enrichment resulted from evaporation in stream and moat samples and from sublimation in surface lake-ice samples. Tritium enrichment resulted from exchange with the postnuclear atmosphere in stream and moat samples. Rapid injection of tritiated water into the upper water column of the make and incorporation of this water into the ice cover resulted in uniformly elevated tritium contents (> 3.0 TU) in these reservoirs. Tritium was also present in deep water, suggesting that a component of bottom water was recently at the surface. During summer, melted lake ice and stream water forms the moat. Water excluded from ice formation during fall moat freezing (enriched in solutes and tritium, and depleted in 18O and 2H relative to water below 15-m depth) may sink as density currents to the bottom of the lake. Seasonal lake circulation, in response to climate-driven surface inflow, is therefore responsible for the distribution of both water isotopes and dissolved solutes in Lake Fryxell.

Stable Carbon Isotope Fractionation during Bacterial Acetylene Fermentation: Potential for Life Detection in Hydrocarbon-Rich Volatiles of Icy Planet(oid)s

PubMed Central

Baesman, Shaun M.; Oremland, Ronald S.

2015-01-01

Abstract We report the first study of stable carbon isotope fractionation during microbial fermentation of acetylene (C2H2) in sediments, sediment enrichments, and bacterial cultures. Kinetic isotope effects (KIEs) averaged 3.7 ± 0.5‰ for slurries prepared with sediment collected at an intertidal mudflat in San Francisco Bay and 2.7 ± 0.2‰ for a pure culture of Pelobacter sp. isolated from these sediments. A similar KIE of 1.8 ± 0.7‰ was obtained for methanogenic enrichments derived from sediment collected at freshwater Searsville Lake, California. However, C2H2 uptake by a highly enriched mixed culture (strain SV7) obtained from Searsville Lake sediments resulted in a larger KIE of 9.0 ± 0.7‰. These are modest KIEs when compared with fractionation observed during oxidation of C1 compounds such as methane and methyl halides but are comparable to results obtained with other C2 compounds. These observations may be useful in distinguishing biologically active processes operating at distant locales in the Solar System where C2H2 is present. These locales include the surface of Saturn's largest moon Titan and the vaporous water- and hydrocarbon-rich jets emanating from Enceladus. Key Words: Acetylene—Fermentation—Isotope fractionation—Enceladus—Life detection. Astrobiology 15, 977–986. PMID:26539733

Carbon isotopic composition of forest soil respiration in the decade following bark beetle and stem girdling disturbances in the Rocky Mountains: Carbon isotopes of soil respiration following disturbance

DOE PAGES

Maurer, Gregory E.; Chan, Allison M.; Trahan, Nicole A.; ...

2016-04-26

Bark beetle outbreaks are widespread in western North American forests, reducing primary productivity and transpiration, leading to forest mortality across large areas and altering ecosystem carbon cycling. Here the carbon isotope composition (δ13C) of soil respiration (δJ) was monitored in the decade after disturbance for forests affected naturally by mountain pine beetle infestation and artificially by stem girdling. The seasonal mean δJ changed along both chronosequences. We found (a) enrichment of δJ relative to controls (<1 ‰) in near-surface soils in the first 2 years after disturbance; (b) depletion (1‰ or no change) during years 3–7; and (c) a secondmore » period of enrichment (1–2‰) in years 8–10. Results were consistent with isotopic patterns associated with the gradual death and decomposition of rhizosphere organisms, fine roots, conifer needles and woody roots and debris over the course of a decade after mortality. Finally, δJ was progressively more 13C-depleted deeper in the soil than near the surface, while the bulk soil followed the well-established pattern of 13C-enrichment at depth. Overall, differences in δJ between mortality classes (<1‰) and soil depths (<3‰) were smaller than variability within a class or depth over a season (up to 6‰).« less

Why is Mineral-Associated Organic Matter Enriched in 15N? Evidence from Grazed Pasture Soil

NASA Astrophysics Data System (ADS)

Baisden, W. T.; Wells, N. S.; Mudge, P. L.; Clough, T. J.; Schipper, L. A.; Ghani, A.; Stevenson, B.

2014-12-01

Throughout the scientific literature, measurements across soil depth and density fractions suggest that, with few exceptions, mineral-associated organic matter (OM) has higher δ15N than non-mineral-associated OM. This implies that the δ15N difference between N inputs and mineral-stabilized OM may characterize the microbial processes involved in stabilization and mineral association. Yet current understanding of observed N isotope fractionation in terrestrial ecosystems suggests the large isotope effects are expressed during inorganic N transformations from NH4 to gaseous loss pathways of NH3 volatilization and denitrification. How can the relative importance of N isotope fractionation during OM stabilization versus loss pathways be resolved? We recently examined N isofluxes when a temporary nitrogen excess is created by urine deposition in a New Zealand dairy pasture. We found that the N isotopic composition of volatilized NH3, and NO3 available for leaching or denitrification could not be linked back to the added N using Rayleigh distillation models. Instead, the results imply that the added N was immobilized, and the N available for losses was increasingly derived from mineralization of organic matter during the course of the experiment. These results are consistent with recent evidence of enhanced OM mineralization in urine patches, understanding of N isotope mass balances and long-standing evidence that gross mineralization and immobilization fluxes greatly exceed net mineralization and nitrification, except at very high N saturation. These results suggest that where 15N enrichment occurs due to fractionating loss pathways, the isotope effects are primarily transmitted to immobilized N, forming 15N enriched stabilized OM. This further explains earlier findings that the δ15N of soil OM represents an integrated indicator of losses, reflecting the intensity and duration of pastoral agriculture. We suggest that development of an indicator based on δ15N in mineral-associated OM might relate mineralization rates to the δ15N of stabilized or immobilized N.

Investigating trophic relationships of pinnipeds in Alaska and Washington using stable isotope ratios of nitrogen and carbon

USGS Publications Warehouse

Hobson, Keith A.; Sease, John L.; Merrick, Richard L.; Piatt, John F.

1997-01-01

We measured stable-nitrogen (δ15N) and stable-carbon (δ13C) isotope ratios in muscle and hair from 7 northern fur seals (Callorhinus ursinus) from the Pribilof Islands, Alaska, and 27 Steller sea lions (Eumetopias jubatus), and 14 harbor seals (Phoca vitulina) from the Gulf of Alaska and coast of Washington State, in order to contrast dietary information derived from isotopic vs. available conventional dietary studies. Stable-nitrogen-isotope analysis of muscle revealed that harbor seals were enriched over sea lions (mean δ15N = 18.6‰vs. 17.5‰) which were in turn enriched over northern fur seals (mean δ15N = 16.6‰). Trophic segregation among these species likely results primarily from differential reliance on herring (Clupea harengus), Atka mackerel (Pleurogrammus monopterygius), and large vs. small walleye pollock (Theregra chalcogramma). According to their δ15N values, adult male Steller sea lions showed a higher trophic position than adult females (mean δ15N: 18.0‰ vs. 17.2‰), whereas adult female northern fur seals were trophically higher than juvenile male fur seals (mean δ15N: 16.5‰vs. 15.0‰). Each of these observed differences likely resulted from differential reliance on squid or differences in the size range of pollock consumed. Three northern fur seal pups showed higher δ15N enrichment over adults (mean 17.7‰vs. 15.8‰) due to their reliance on their mother's milk. Stable-carbon isotope measurements of hair revealed a cline toward more negative values with latitude. Segregation in hair δ13C between Steller sea lions and harbor seals off the coast of Washington (mean δ13C: -13.6‰ vs. -15.0‰) reflected the greater association of harbor seals with freshwater input from the Columbia River. Our study demonstrates the utility of the stable isotope approach to augment conventional dietary analyses of pinnipeds and other marine mammals.

Packed bed reactor for photochemical .sup.196 Hg isotope separation

DOEpatents

Grossman, Mark W.; Speer, Richard

1992-01-01

Straight tubes and randomly oriented pieces of tubing having been employed in a photochemical mercury enrichment reactor and have been found to improve the enrichment factor (E) and utilization (U) compared to a non-packed reactor. One preferred embodiment of this system uses a moving bed (via gravity) for random packing.

Comparison of different mass spectrometry techniques in the measurement of L-[ring-13C6]phenylalanine incorporation into mixed muscle proteins

PubMed Central

Zabielski, Piotr; Ford, G. Charles; Persson, X. Mai; Jaleel, Abdul; Dewey, Jerry D.; Nair, K Sreekumaran

2013-01-01

Precise measurement of low enrichment of stable isotope labeled amino-acid tracers in tissue samples is a prerequisite in measuring tissue protein synthesis rates. The challenge of this analysis is augmented when small sample size is a critical factor. Muscle samples from human participants following an 8 hour intravenous infusion of L-[ring-13C6]phenylalanine and a bolus dose of L-[ring-13C6]phenylalanine in a mouse were utilized. Liquid Chromatography tandem mass spectrometry (LC/MS/MS), Gas Chromatography tandem mass spectrometry (GC/MS/MS) and Gas Chromatography/Mass spectrometry (GC/MS) were compared to the Gas Chromatography-Combustion-Isotope Ratio mass spectrometry (GC/C/IRMS), to measure mixed muscle protein enrichment of [ring13C6]phenylalanine enrichment. The sample isotope enrichment ranged from 0.0091 to 0.1312 Molar Percent excess (MPE). As compared with GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS showed coefficients of determination of R2 = 0.9962 and R2 = 0.9942, and 0.9217 respectively. However, the precision of measurements (coefficients of variation) for intra-assay are 13.0%, 1.7%, 6.3% and 13.5% and for inter-assay are 9.2%, 3.2%, 10.2% and 25% for GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS respectively. The muscle sample sizes required to obtain these results were 8μg, 0.8μg, 3μg and 3μg for GC/C/IRMS, LC/MS/MS, GC/MS/MS, and GC/MS respectively. We conclude that LC/MS/MS is optimally suited for precise measurements of L-[ring-13C6]phenylalanine tracer enrichment in low abundance and in small quantity samples. PMID:23378099

Extremely 54Cr- and 50Ti-rich Presolar Oxide Grains in a Primitive Meteorite: Formation in Rare Types of Supernovae and Implications for the Astrophysical Context of Solar System Birth

NASA Astrophysics Data System (ADS)

Nittler, Larry R.; O’D. Alexander, Conel M.; Liu, Nan; Wang, Jianhua

2018-04-01

We report the identification of 19 presolar oxide grains from the Orgueil CI meteorite with substantial enrichments in 54Cr, with 54Cr/52Cr ratios ranging from 1.2 to 56 times the solar value. The most enriched grains also exhibit enrichments at mass-50, most likely due in part to 50Ti, but close-to-normal or depleted 53Cr/52Cr ratios. There is a strong inverse relationship between 54Cr enrichment and grain size; the most extreme grains are all <80 nm in diameter. Comparison of the isotopic data with predictions of nucleosynthesis calculations indicate that these grains most likely originated in either rare, high-density Type Ia supernovae (SN Ia), or in electron-capture supernovae (ECSN), which may occur as the end stage of evolution for stars of mass 8–10 M ⊙. This is the first evidence for preserved presolar grains from either type of supernova. An ECSN origin is attractive, as these likely occur much more frequently than high-density SN Ia, and their evolutionary timescales (∼20 Myr) are comparable to those of molecular clouds. Self-pollution of the Sun’s parent cloud from an ECSN may explain the heterogeneous distribution of n-rich isotopic anomalies in planetary materials, including a recently reported dichotomy in Mo isotopes in the solar system. The stellar origins of three grains with solar 54Cr/52Cr, but anomalies in 50Cr or 53Cr, as well as of a grain enriched in 57Fe, are unclear.

Deep electromagnetic sounding of the moon with Lunokhod 2 data

NASA Technical Reports Server (NTRS)

Vanyan, L. L.; Yegorov, I. V.; Faynberg, E. B.

1977-01-01

Results of electromagnetic sounding distinguished an outer high resistance shell about 200 km thick in the moon's structure. A preliminary petrological interpretation of the moon's layers indicated their origin as a consequence of differentiation of the initial peridotite material. Upon melting, 20% to 40% of the material melts and is removed to form a high resistance basaltic shell underlain by a layer of spinal peridotites enriched in divalent iron oxides and having a reduced resistance.

Elucidating MTBE degradation in a mixed consortium using a multidisciplinary approach.

PubMed

Bastida, Felipe; Rosell, Mònica; Franchini, Alessandro G; Seifert, Jana; Finsterbusch, Stefanie; Jehmlich, Nico; Jechalke, Sven; von Bergen, Martin; Richnow, Hans H

2010-08-01

The structure and function of a microbial community capable of biodegrading methyl-tert-butyl ether (MTBE) was characterized using compound-specific stable isotope analysis (CSIA), clone libraries and stable isotope probing of proteins (Protein-SIP). The enrichment culture (US3-M), which originated from a gasoline-impacted site in the United States, has been enriched on MTBE as the sole carbon source. The slope of isotopic enrichment factors (epsilon(C) of -2.29+/-0.03 per thousand; epsilon(H) of -58+/-6 per thousand) for carbon and hydrogen discrimination (Deltadelta(2)H/Deltadelta(13)C) was on average equal to Lambda=24+/-2, a value closely related to the reaction mechanism of MTBE degradation in Methylibium petroleiphilum PM1. 16S rRNA gene libraries revealed sequences belonging to M. petroleiphilum PM1, Hydrogenophaga sp., Thiothrix unzii, Rhodobacter sp., Nocardiodes sp. and different Sphingomonadaceae bacteria. Protein-SIP analysis of the culture grown on (13)C-MTBE as the only carbon source revealed that proteins related to members of the Comamonadaceae family, such as Delftia acidovorans, Acidovorax sp. or Comamonas sp., were not (13)C-enriched, whereas proteins related to M. petroleiphilum PM1 showed an average incorporation of 94.5 atom%(13)C. These results indicate a key role for this species in the degradation of MTBE within the US3-M consortia. The combination of CSIA, molecular biology and Protein-SIP facilitated the analysis of an MTBE-degrading mixed culture from a functional and phylogenetic point of view.

The source of dissolved silicon in soil surface solutions of a temperate forest ecosystem: Ge/Si and Si isotope ratios as biogeochemical tracers

NASA Astrophysics Data System (ADS)

Cornelis, J.; Delvaux, B.; Cardinal, D.; André, L.; Ranger, J.; Opfergelt, S.

2010-12-01

Understand the biogeochemical cycle of silicon (Si) in the Earth’s critical zone and the dissolved Si transfer from the litho-pedosphere into the hydrosphere is of great interest for the global balance of biogeochemical processes, including the global C cycle. Indeed, the interaction between Si and C cycles regulates the atmospheric CO2 through the chemical weathering of silicate minerals, the C sequestration in stable organo-mineral compounds and the Si nutrition of phytoplankton CO2-consumers in oceans. H4SiO4 released by mineral dissolution contributes to the critical zone evolution through neoformation of secondary minerals, adsorption onto hydroxyl-bearing phases and recycling by vegetation and return of phytoliths on topsoil. The neoformation of secondary precipitates (clay minerals and phytoliths polymerized in plants) and adsorption of Si onto Fe and Al (hydr)oxides are processes favoring the light Si isotope incorporation, generating rivers enriched in heavy Si isotopes. On the other hand, clay minerals and phytoliths display contrasting Ge/Si ratios since clay-sized weathering products are enriched in Ge and phytoliths are depleted in Ge. Thus stable Si isotope and Ge/Si ratios constitute very interesting proxies to trace transfer of Si in the critical zone. Here we report Si isotopic and Ge/Si ratios of the different Si pools in a temperate soil-tree system (Breuil experimental forest, France) involving various tree species grown on Alumnic Cambisol derived from granitic bedrock. Relative to granitic bedrock (δ30Si = -0.07 ‰; Ge/Si = 2.5 µmol/mol), clay-sized minerals are enriched in 28Si (-1.07 ‰) and Ge (6.2 µmol/mol) while phytoliths are enriched in 28Si (-0.28 to -0.64 ‰) and depleted in Ge (0.1 to 0.3 µmol/mol). This contrast allows us to infer the relative contribution of litho/pedogenic and biogenic mineral dissolution on the release of H4SiO4 in soil surface solutions. The Si-isotope signatures and Ge/Si ratios of forest floor solutions evolve towards lighter values (-1.38 and -2.05 ‰) and higher Ge/Si ratios (2.7 µmol/mol) relative to granite bedrock. This suggests a partial dissolution of 28Si and Ge-enriched secondary clays minerals incorporated by bioturbation in organic-rich horizons, with a fractionation releasing preferentially light Si isotopes. Without considering that organic acids promote dissolution of minerals, clay minerals detected in the organic layer (vermiculite, chlorite, illite and Ca-montmorillonite) are not stable and could have been partially dissolved and transformed in the chemical environment of forest floor. Sources of H4SiO4 in forest floor solutions are influenced by tree species which control the extent of clay-sized minerals mixed in organic horizons by bioturbation and, to a lesser extent, the Si recycling by forest vegetation.

Large fractionations of C and H isotopes related to methane oxidation in Arctic lakes

NASA Astrophysics Data System (ADS)

Cadieux, Sarah B.; White, Jeffrey R.; Sauer, Peter E.; Peng, Yongbo; Goldman, Amy E.; Pratt, Lisa M.

2016-08-01

Microbial oxidation of methane (CH4) plays a central role in carbon cycling in Arctic lakes, reducing potential CH4 emissions associated with warming. Isotopic signatures of CH4 (δ13C and δ2H) are indicators of microbial oxidation, wherein the process strongly enriches 13C and 2H in residual CH4. We present δ13C and δ2H measurements obtained from sampling the water column and sediment for dissolved CH4 from three, small Arctic lakes in western Greenland under both open-water and ice-covered conditions from 2013 to 2014. Despite substantial variations in aquatic chemistry among the lakes, δ13C and δ2H of CH4 suggested that CH4 was produced predominantly by acetoclastic methanogenesis in the littoral sediments and hydrogenotrophic methanogenesis in the profundal sediments in all of the lakes. Surprisingly large variations for both δ13C and δ2H of CH4 were observed, with δ13C extending from -72‰ to +7.4‰ and δ2H from -390‰ to +250‰. The CH4 isotopic values reported here were significantly more enriched (p < 0.0001) in both 13C and 2H than values reported from other Arctic freshwater environments. As is characteristic of methanotrophy, the enrichment in 13C and 2H was associated with low CH4 concentrations. We suggest that the CH4 most enriched in 13C and 2H may reflect unusually efficient methanotrophic communities in Arctic ice-margin lakes. This study provides the first measurement of δ2H for CH4 in an Arctic freshwater environment at concentrations <10 μM. The extreme enrichment of 13C and 2H of CH4 from Arctic methanotrophy has significant implications for interpreting sources and sinks of CH4. Without knowledge of local geology, stable isotope values of CH4 higher than -30‰ for δ13C and -150‰ for δ2H could be misinterpreted as thermogenic, geothermal, or abiogenic origins. Given crystalline bedrock and the strong positive correlation between δ13C and δ2H throughout the water columns in three Arctic lakes confirms that CH4 heavily enriched in 13C and 2H is the result of methanotrophy.

C isotope fractionation during heterotrophic activity driven carbonate precipitation

NASA Astrophysics Data System (ADS)

Balci, Nurgul; Demirel, Cansu

2016-04-01

Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate precipitation inthe hypersaline Lake Acıgöl (Turkey) with microbial cultures. Geomicrobiology Journal DOI: 10.1080/01490451.2015.1099763. TUBITAK (The Scientific and Technological Research Council of Turkey) Grant to N. BALCI (113Y464).

Silylated Derivatives Retain Carbon and Alter Expected 13C-Tracer Enrichments Using Continuous Flow-Combustion-Isotope Ratio Mass Spectrometry

PubMed Central

Shinebarger, Steven R.; Haisch, Michael; Matthews, Dwight E.

2008-01-01

Continuous-flow inlets from oxidation reactors are commonly used systems for biological sample introduction into isotope ratio mass spectrometers (IRMS) to measure 13C enrichment above natural abundance. Because the samples must be volatile enough to pass through a gas chromatograph, silylated derivatization reactions are commonly used to modify biological molecules to add the necessary volatility. Addition of a t-butyldimethylsilyl (TBDMS) group is a common derivatization approach. However, we have found that samples do not produce the expected increment in measured 13C abundance as the TBDMS derivatives. We have made measurements of 13C enrichment of leucine and glutamate standards of known 13C enrichment using derivatives without silicon (N-acetyl n-propyl ester), with silicon (TBDMS), and an intermediate case. The measurements of 13C in amino acids derivatized without silicon were as expected. The 13C enrichment measurements using the TBDMS derivative were higher than expected, but could be corrected to produce the expected 13C enrichment measurement by IRMS if one carbon was removed per silicon. We postulate that the silicon in the derivative forms silicon carbide compounds in the heated cupric oxide reactor, rather than forming silicon dioxide. Doing so reduces the amount of CO2 formed from the carbon in the sample. Silylated derivatives retain carbon with the silicon and must be used carefully and with correction factors to measure 13C enrichments by continuous-flow IRMS. PMID:12510745

Magnesium isotope fractionation between brucite [Mg(OH)2] and Mg aqueous species: Implications for silicate weathering and biogeochemical processes

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Beard, Brian L.; Li, Chengxiang; Johnson, Clark M.

2014-05-01

Brucite, with its octahedral structure, has a lattice configuration that is similar to the Mg-bearing octahedral layers in phyllosilicates. Understanding stable Mg isotope fractionation between brucite and aqueous solution therefore bears on interpretation of Mg isotope data in natural weathering systems. In this study, we experimentally determined Mg isotope fractionation between brucite and two Mg aqueous species, the free Mg aquo ion ([Mg(OH2)6]2+) and EDTA-bonded Mg (Mg-EDTA2-). Results from recrystallization and brucite synthesis experiments suggest mild preferential partitioning of light Mg isotopes into brucite compared to Mg aquo ions at low temperatures, where measured ΔMgbrucite-Mg26 fractionation increased from ca. -0.3‰ at 7 °C, to ca. -0.2‰ at 22 °C, to ca. 0‰ at 40 °C. MgO hydrolysis experiments in EDTA-bearing solutions suggest that the ΔMgbrucite-Mg-EDTA26 fractionation is ⩾+2.0‰ at 22 °C, indicating that light Mg isotopes strongly partition into Mg-EDTA complex relative to brucite, as well as relative to Mg aquo ions. Magnesium atoms in brucite, Mg aquo ions, and Mg-EDTA complexes are all octahedrally coordinated, and the measured Mg isotope fractionations correlate with average bond lengths for Mg. Aqueous Mg ions have the shortest bond length among the three phases, and enrich heavy Mg isotopes relative to brucite and Mg-EDTA. In contrast, Mg-EDTA has the longest average bond length for Mg, and enriches light Mg isotopes relative to Mg aquo ions and brucite; the relatively long Mg-EDTA bond suggests that organically bound Mg may commonly have low 26Mg/24Mg ratios, which may explain proposed "vital" effects for stable Mg isotopes. Such relations between bond length and Mg isotope fractionation could be extended to other phyllosilicates such as serpentine- and clay-group minerals where Mg is also octahedrally coordinated.

The fate of moderately volatile elements during planetary formation in the inner Solar System

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2017-12-01

Moderately volatile element abundances are variable among inner Solar System bodies, with differing degrees of depletion compared to chondrites. These variations are a consequence of the processes of planetary formation. The conditions and the specific mechanisms of planetary accretion and differentiation can be investigated by analyzing the stable isotope compositions of terrestrial and extraterrestrial samples. The moderately volatile lithophile elements are particularly useful to distinguish between the effects of accretion and those of core formation. Recent work has shown isotope variations in inner Solar System bodies for the moderately volatile elements Zn and K. The purely lithophile nature of Rb (in contrast to Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to further study moderately volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. Terrestrial rocks define a narrow range in Rb isotope composition, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). Larger Rb isotope variations are observed in extraterrestrial materials. Carbonaceous chondrites display a trend toward lighter Rb isotope composition coupled with decreasing Rb/Sr, opposite to the effect expected if their volatile element variations were caused by evaporative loss of Rb. This relationship indicates that the volatile element abundance variations in carbonaceous chondrites are not due to evaporation or condensation, but rather are due to the mixing of chemically and isotopically distinct primordial reservoirs. In contrast, there is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. Significant heavy isotope enrichments (up to several per mil for 87Rb/85Rb) are found for volatile-depleted planetesimals, including eucrites. In addition, lunar rocks also display heavy Rb isotope enrichments compared to the BSE. The most likely cause of these variations is Rb isotope fractionation due to evaporation during accretion.

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Silicon isotopes reveal recycled altered oceanic crust in the mantle sources of Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, Emily A.; Moynier, Frédéric; Savage, Paul S.; Jackson, Matthew G.; Moreira, Manuel; Day, James M. D.

2016-09-01

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (∼several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (∼tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen. Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. On average, δ30Si values for OIB (-0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (-0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (δ30Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources.

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

PubMed

Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

2015-07-15

We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the calibration requirements are met), LC/IRMS is the technique of choice. The reasons for this are the improved precision, simpler sample preparation, and straightforward isotopic calibration. Copyright © 2015 John Wiley & Sons, Ltd.

Evolution of the upper mantle beneath the southern Baikal rift zone: an Sr-Nd isotope study of xenoliths from the Bartoy volcanoes

NASA Astrophysics Data System (ADS)

Ionov, D. A.; Kramm, U.; Stosch, H.-G.

1992-06-01

Anhydrous and amphibole-bearing peridotite xenoliths occur in roughly equal quantitites in the Bartoy volcanic field about 100 km south of the southern tip of Lake Baikal in Siberia (Russia). Whole-rock samples and pure mineral separates from nine xenoliths have been analyzed for Sr and Nd isotopes in order to characterize the upper mantle beneath the southern Baikal rift zone. In an Sr-Nd isotope diagram both dry and hydrous xenoliths from Bartoy plot at the junction between the fields of MORB and ocean island basalts. This contrasts with data available on two other localities around Lake Baikal (Tariat and Vitim) where peridotites typically have Sr-Nd isotope compositions indicative of strong long-term depletion in incompatible elements. Our data indicate significant chemical and isotopic heterogeneity in the mantle beneath Bartoy that may be attributed to its position close to an ancient suture zone separating the Siberian Platform from the Mongol-Okhotsk mobile belt and occupied now by the Baikal rift. Two peridotites have clinopyroxenes depleted in light rare earth elements (LREE) with Sr and Nd model ages of about 2 Ga and seem to retain the trace element and isotopic signatures of old depleted lithospheric mantle, while all other xenoliths show different degrees of LREE-enrichment. Amphiboles and clinopyroxenes in the hydrous peridotites are in Sr-Nd isotopic disequilibrium. If this reflects in situ decay of 147Sm and 87Rb rather than heterogeneities produced by recent metasomatic formation of amphiboles then 300 400 Ma have passed since the minerals were last in equilibrium. This age range then indicates an old enrichment episode or repeated events during the Paleozoic in the lithospheric mantle initially depleted maybe ˜2 Ga ago. The Bartoy hydrous and enriched dry peridotites, therefore, are unlikely to represent fragments of a young asthenospheric bulge which, according to seismic reflection studies, reached the Moho at the axis of the Baikal rift zone a few Ma ago. By contrast, hydrous veins in peridotites may be associated with rift formation processes.

Evaluating Crustal Contamination Effects on the Lithophile Trace Element Budget of Shergottites

NASA Technical Reports Server (NTRS)

Brandon, A. D.; Ferdous, J.; Peslier, A. H.

2017-01-01

The origin of the incompatible trace element (ITE) enriched compositions of shergottites has been a point of contention for decades [1-2]. Two scenarios have been proposed, the first is that enriched shergottite compositions reflect an ITE-enriched mantle source, whereas in the second, the ITE enrichment reflects crustal contamination of mantle-derived parent magmas. Evidence supporting the first scenario is that the ITE-enriched shergottite compositions are consistent with the outcomes of magma ocean crystallization [3], and that Os-Nd isotope relationships for shergottites cannot be explained by realistic crustal contamination models [4]. In contrast, Cl and S isotopes are consistent with shergottite magmas interacting with Mars crust [5,6], and ITE-enriched olivine-hosted melt inclusions and interstitial glass are found in depleted shergottite Yamato 980459 [7]. These findings indicate that some level of crustal interaction occurred but the question of whether ITE-enrichments in some bulk shergottites reflect crustal contamination remains open. Recently, a Mars crustal breccia meteorite has been found, NWA 7034 and its paired stones, that is our best analogue to an average of Mars ancient crust [8-10]. This allows for better constraints on crustal contamination of shergottite magmas. We modeled magma-crust mixing and assimilation-fractional crystallization (AFC) using ITE-depleted shergottite compositions and bulk NWA 7034 and its clasts as end-members. The results of these models indicate that crustal contamination can only explain the ITE-enriched compositions of some bulk shergottites under unusual circumstances. It is thus likely that the shergottite range of compositions reflects primarily mantle sources.

Evidence of hydraulic lift for pre-rainy season leaf out and dry-season stem water enrichment in Sclerocarya birrea, a tropical agroforestry tree

NASA Astrophysics Data System (ADS)

Ceperley, Natalie; Mande, Theophile; Rinaldo, Andrea; Parlange, Marc B.

2014-05-01

We use stable isotopes of water as tracers to follow water use by five Sclerocarya birrea trees in a catchment in South Eastern Burkina Faso interspersed with millet fields, gallery forest, Sudanian savanna, and fallow fields. Isotopic ratios were determined from water extracted from stems of the trees and sub-canopy soil of two of them, while nearby ground water, precipitation, and surface water was sampled weekly. A unique configuration of sensors connected with a wireless sensor network of meteorological stations measured sub-canopy shading, the temperature and humidity in the canopy, through-fall, and soil moisture under two of the trees. Both water extracted from sap and water extracted from soil is extremely enriched in the dry season, but drop to levels close to the ground water in February or March, which coincides with the growth of leaves. Dates of leaf out were confirmed by changes in δDH and δO18 concentrations of water, photographic documentation & pixel analysis, and analysis of sub-canopy radiation and proceeded the rise in humidity and flow that was later detected in the sub-canopy soil, the trunk of the tree (sap-flow), and atmosphere (canopy VPD). Examination of the isotopic signature suggests that size of tree plays an important role in duration and timing of this leaf-out as well as the degree of enrichment during the peak of the dry season. Further examination of the isotopic signatures of the roots suggested that the trees are performing hydraulic redistribution, or lifting the ground water and "sharing it" with the soil in the rooting zone in the dry season. The enriched level of xylem in this case is a product of water loss, and enrichment, along the travel path of the water from the roots to the tip of the stem, as evidenced by the variation according to size of tree. Vapor pressure deficit, soil water, and soil moisture interactions support this picture of interacting controls, separate from hydrologic triggers on the water movement in the tree.

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

PubMed

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

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.

Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Cartigny, Pierre

2010-01-01

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665-667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ˜ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid-rock interaction and to immiscibility processes. Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

The variations of d30Si values in diagenetic chert and chert- associated BIFs over time can be used to reconstruct the environmental conditions of the early Earth, and become a hot topic in the Si isotope society. However, there are several different views of explaining the variation of d30Si values over time. Moreover, there are disputes in explaining the distribution of Si isotope in several main reservoirs in surface systems. Those disagreements are caused by lacking key Si isotope fractionation factors associated with the formation processes of chert and its altered products. There are many unexplained observations about Si isotope distributions in Earth's surface systems (Opfergelt and Delmelle, 2012). For example, the deduced Si isotope equilibrium fractionation factors by Rayleigh model at ambient temperature between clay and the solution D30Siclay-solution = -1.5 ‰ and -2.05 ‰ (Hughes et al., 2013) obviously disagree with common sense, which dictates that stiffer chemical bonds will enrich heavier isotopes, i.e., the precipitated minerals will preferentially incorporate heavy isotopes relative to aqueous H4SiO4 due to their shorter Si-O bonds. Another similar case is the fractionation between quartz and solution. Most field observations suggested that solution will be enriched with heavier Si isotope compared to quartz, conflicting to the fact that quartz is the one with much shorter Si-O bonds than aqueous H4SiO4 (ca. 1.610Å vs. 1.639Å). Here we provide equilibrium and kinetic Si isotope fractionation factors associated with the formation of amorphous quartz and other secondary minerals in polymerization, co-precipitation and adsorption processes. The adsorption processes of silica gel to Fe-hydroxides have been carefully examined. The Si isotope fractionations due to the formation of mono-dentate to quadru-dentate adsorbed Fe-Si complexes have been calculated. These data can explain well the experimental observations (e.g., Zheng et al., 2016) and provide further insights into such processes. With the knowledge of Si isotope fractionations of those processes, we can quantitatively evaluate the net Si isotope fractionation during the chert formation processes and can link the Si isotope composition of chert to that of seawater from now to early Archean.

Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

NASA Astrophysics Data System (ADS)

Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

2016-12-01

Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen isotope exchange between extracellular CH4 and H2O through reversible reactions of the microbial methanogenic pathway in methanogenic region and/or geological methane reservoirs.

Three-dimensional imaging of cholesterol and sphingolipids within a Madin-Darby canine kidney cell

DOE PAGES

Yeager, Ashley N.; Weber, Peter K.; Kraft, Mary L.

2016-01-08

Metabolic stable isotope incorporation and secondary ion mass spectrometry(SIMS) depth profiling performed on a Cameca NanoSIMS 50 were used to image the 18O-cholesterol and 15N-sphingolipid distributions within a portion of a Madin-Darby canine kidney (MDCK) cell. Three-dimensional representations of the component-specific isotope distributions show clearly defined regions of 18O-cholesterol and 15N-sphingolipid enrichment that seem to be separate subcellular compartments. Furthermore, the low levels of nitrogen-containing secondary ions detected at the 18O-enriched regions suggest that these 18O-cholesterol-rich structures may be lipiddroplets, which have a core consisting of cholesterol esters and triacylglycerides.

Three-dimensional imaging of cholesterol and sphingolipids within a Madin-Darby canine kidney cell

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

Yeager, Ashley N.; Weber, Peter K.; Kraft, Mary L.

Metabolic stable isotope incorporation and secondary ion mass spectrometry(SIMS) depth profiling performed on a Cameca NanoSIMS 50 were used to image the 18O-cholesterol and 15N-sphingolipid distributions within a portion of a Madin-Darby canine kidney (MDCK) cell. Three-dimensional representations of the component-specific isotope distributions show clearly defined regions of 18O-cholesterol and 15N-sphingolipid enrichment that seem to be separate subcellular compartments. Furthermore, the low levels of nitrogen-containing secondary ions detected at the 18O-enriched regions suggest that these 18O-cholesterol-rich structures may be lipiddroplets, which have a core consisting of cholesterol esters and triacylglycerides.

Evaluation of excitation functions of proton and deuteron induced reactions on enriched tellurium isotopes with special relevance to the production of iodine-124.

PubMed

Aslam, M N; Sudár, S; Hussain, M; Malik, A A; Shah, H A; Qaim, S M

2010-09-01

Cross-section data for the production of medically important radionuclide (124)I via five proton and deuteron induced reactions on enriched tellurium isotopes were evaluated. The nuclear model codes, STAPRE, EMPIRE and TALYS, were used for consistency checks of the experimental data. Recommended excitation functions were derived using a well-defined statistical procedure. Therefrom integral yields were calculated. The various production routes of (124)I were compared. Presently the (124)Te(p,n)(124)I reaction is the method of choice; however, the (125)Te(p,2n)(124)I reaction also appears to have great potential.

METHOD OF AND APPARATUS FOR WITHDRAWING LIGHT ISOTOPIC PRODUCT FROM A LIQUID THERMAL DIFFUSION PLANT

DOEpatents

Dole, M.

1959-09-22

An improved process and apparatus are described for removing enriched product from the columns of a thermal diffusion plant for separation of isotopes. In the removal cycle, light product at the top cf the diffusion columns is circulated through the column tops and a shipping cylinder connected thereto unttl the concertation of enriched product in the cylinder reaches the desired point. During the removal, circulation through the bottoms is blocked bv freezing. in the diffusion cycle, the bottom portion is unfrozen, fresh feed is distributed to the bottoms of the columns, ard heavy product is withdrawn from the bottoms, while the tops of the columns are blocked by freezing.

Persistence of fertile and hydrous lithospheric mantle beneath the northwestern Ethiopian plateau: Evidence from modal, trace element and Sr-Nd-Hf isotopic compositions of amphibole-bearing mantle xenoliths

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Aulbach, Sonja

2017-07-01

We present new trace element compositions of amphiboles, Sr-Nd-Hf isotope compositions of clinopyroxenes and mineral modes for spinel peridotite xenoliths that were entrained in a Miocene alkali basalt (Gundeweyn, northwestern Ethiopian plateau), in order to understand the geochemical evolution and variation occurring within the continental lithospheric mantle (CLM) in close proximity to the East African Rift system, and its dynamic implications. With the exception of a single amphibole-bearing sample that is depleted in LREE (La/YbN = 0.45 × Cl), amphiboles in lherzolites and in one harzburgite show variable degrees of LREE enrichment (La/YbN = 2.5-12.1 × Cl) with flat HREE (Dy/YbN = 1.5-2.1 × Cl). Lherzolitic clinoyroxenes have 87Sr/86Sr (0.70227 to 0.70357), 143Nd/144Nd (0.51285 to 0.51346), and 176Hf/177Hf (0.28297 to 0.28360) ranging between depleted lithosphere and enriched mantle. LREE-enriched clinopyroxenes generally have more enriched isotope compositions than depleted ones. While lherzolites with isotope compositions similar to those of the Afar plume result from the most recent metasomatic overprint, isotope compositions more depleted than present-day MORB can be explained by an older melt extraction and/or isotopic rehomogenisation event, possibly related to the Pan-African orogeny. Several generations of amphibole are recognized in accord with this multi-stage evolution. Texturally unequilibrated amphibole occurring within the peridotite matrix and in melt pockets attest to continued hydration and refertilization of the lithospheric mantle subsequent to Oligocene flood basalt magmatism, during which an earlier-emplaced inventory of amphibole was likely largely consumed. However, a single harzburgite contains amphibole with the highest Mg# and lowest TiO2 content, which is interpreted as sampling a volumetrically subordinate mantle region beneath the Ethiopian plateau that was not tapped during flood basalt magmatism. Strikingly, both trace-element enriched and depleted lherzolites have high clinopyroxene and orthopyroxene and low olivine contents (median 15, 24 and 56 vol.%), combined with primitive olivine Mg# (median 89.5), indicating the presence of refertilized mantle beneath Gundeweyn. Despite its fertility and FeO-rich character (hence high inferred density), and impingement by the Afar plume, the CLM beneath the Ethiopian plateau, though apparently thinned through thermochemical erosion, has so far resisted whole-sale delamination or dripping. This is tentatively ascribed to insufficient stress and density contrasts at the periphery of the Afar plume, which reached its greatest thermochemical buoyancy in the Afar region, northeast of Gundeweyn.

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2010 CFR

2010-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2012 CFR

2012-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2011 CFR

2011-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2013 CFR

2013-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2014 CFR

2014-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

PubMed

Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

2015-01-01

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio measurements. However, data obtained in this study show that instrumental mass discrimination in MC-ICP-MS is consistent with mass-dependent Mo isotope fractionation. This was demonstrated by a good agreement between experimentally obtained and theoretically expected values of the exponent of isotope fractionation, β, for each triad of Mo isotopes.

High accuracy method for the application of isotope dilution to gas chromatography/mass spectrometric analysis of gases.

PubMed

Milton, Martin J T; Wang, Jian

2003-01-01

A new isotope dilution mass spectrometry (IDMS) method for high-accuracy quantitative analysis of gases has been developed and validated by the analysis of standard mixtures of carbon dioxide in nitrogen. The method does not require certified isotopic reference materials and does not require direct measurements of the highly enriched spike. The relative uncertainty of the method is shown to be 0.2%. Reproduced with the permission of Her Majesty's Stationery Office. Copyright Crown copyright 2003.

IMPROVED ION-PRODUCING MECHANISM FOR CALUTRONS

DOEpatents

Bell, W.A. Jr.; Prater, W.K.

1963-12-24

An ion source for electromagnetically operated equipment for the separation of isotopes, such as the Calutron, wherein a unitized construction is employed to house both the arc chamber and the oven chamber to facilitate assembly and maintenance and to improve operation. ( LAMBDA EC)

Uncovering trophic positions and food resources of soil animals using bulk natural stable isotope composition.

PubMed

Potapov, Anton M; Tiunov, Alexei V; Scheu, Stefan

2018-06-19

Despite the major importance of soil biota in nutrient and energy fluxes, interactions in soil food webs are poorly understood. Here we provide an overview of recent advances in uncovering the trophic structure of soil food webs using natural variations in stable isotope ratios. We discuss approaches of application, normalization and interpretation of stable isotope ratios along with methodological pitfalls. Analysis of published data from temperate forest ecosystems is used to outline emerging concepts and perspectives in soil food web research. In contrast to aboveground and aquatic food webs, trophic fractionation at the basal level of detrital food webs is large for carbon and small for nitrogen stable isotopes. Virtually all soil animals are enriched in 13 C as compared to plant litter. This 'detrital shift' likely reflects preferential uptake of 13 C-enriched microbial biomass and underlines the importance of microorganisms, in contrast to dead plant material, as a major food resource for the soil animal community. Soil organic matter is enriched in 15 N and 13 C relative to leaf litter. Decomposers inhabiting mineral soil layers therefore might be enriched in 15 N resulting in overlap in isotope ratios between soil-dwelling detritivores and litter-dwelling predators. By contrast, 13 C content varies little between detritivores in upper litter and in mineral soil, suggesting that they rely on similar basal resources, i.e. little decomposed organic matter. Comparing vertical isotope gradients in animals and in basal resources can be a valuable tool to assess trophic interactions and dynamics of organic matter in soil. As indicated by stable isotope composition, direct feeding on living plant material as well as on mycorrhizal fungi is likely rare among soil invertebrates. Plant carbon is taken up predominantly by saprotrophic microorganisms and channelled to higher trophic levels of the soil food web. However, feeding on photoautotrophic microorganisms and non-vascular plants may play an important role in fuelling soil food webs. The trophic niche of most high-rank animal taxa spans at least two trophic levels, implying the use of a wide range of resources. Therefore, to identify trophic species and links in food webs, low-rank taxonomic identification is required. Despite overlap in feeding strategies, stable isotope composition of the high-rank taxonomic groups reflects differences in trophic level and in the use of basal resources. Different taxonomic groups of predators and decomposers are likely linked to different pools of organic matter in soil, suggesting different functional roles and indicating that trophic niches in soil animal communities are phylogenetically structured. During last two decades studies using stable isotope analysis have elucidated the trophic structure of soil communities, clarified basal food resources of the soil food web and revealed links between above- and belowground ecosystem compartments. Extending the use of stable isotope analysis to a wider range of soil-dwelling organisms, including microfauna, and a larger array of ecosystems provides the perspective of a comprehensive understanding of the structure and functioning of soil food webs. © 2018 Cambridge Philosophical Society.

Stable isotope and microbial analyses of methane-producing process in a geothermal aquifer associated with the subsurface of the accretionary prism, Japan

NASA Astrophysics Data System (ADS)

Hattori, S.; Kimura, H.; Nashimoto, H.; Koba, K.; Yamada, K.; Shimizu, M.; Watanabe, H.; Yoh, M.; Yoshida, N.

2009-04-01

The sedimentary layer in the southern part of Japan is accretionary prism which includes enriched organic materials derived from sediment on oceanic plate. There is geothermal aquifer in which a large amount of methane (CH4) dissolved. Since CH4 is important as a greenhouse gas and an important natural gas fuel, revealing CH4-producing process in subsurface environment is required. To understand the process of the CH4 production, we collected the groundwater from the aquifer of 1,189-1,489 m depth, and analyzed by using stable isotope and microbial analyses. 16S rRNA gene analysis showed a dominancy of hydrogenotrophic methanogens in domain Archaea and a dominancy of anaerobic heterotrophes to be known to produce H2 and CO2 by fermentation process in domain Bacteria. The anaerobic enrichment cultures with the groundwater amended with organic substrates showed that CH4 was produced by co-culture between the fermenters and hydrogenotrophic methanogens. On the other hand, conventional isotopic estimations for the origin of CH4 using δ13C-CH4 and δD-CH4 as well as δ13C-CH4and molecular ratio of C1/(C2+C3) indicated that CH4 was derived from thermogenic pathway. The values of δ13C-CO2, however, had higher values and carbon isotope fractionation factors between CH4 and CO2(α(CO2-CH4)) were approximately 1.05 to 1.06 indicating the possibility of biogenic CH4 production. Therefore, the origin of CH4 production was estimated as mixing both thermogenic and CO2 reduction from isotopic data. Furthermore, we incubated these enriched co-cultures and measure stable carbon isotope ratios of CH4 and CO2 and stable hydrogen isotope ratios of H2O and CH4. We revealed that concentration of H2 were kept lower by these co-cultures between fermenters and hydrogenotrophic methanogens and α(CO2-CH4) values were higher than that of cultures with the ground water amended with high concentration of H2+ CO2. Hydrogen isotope fractionation factor between H2O and CH4 by these co-culture increased (αH values decreased) with increasing H2 concentration.

Changes in δ(13)C of dark respired CO2 and organic matter of different organs during early ontogeny in peanut plants.

PubMed

Ghashghaie, Jaleh; Badeck, Franz W; Girardin, Cyril; Sketriené, Diana; Lamothe-Sibold, Marlène; Werner, Roland A

2015-01-01

Carbon isotope composition in respired CO2 and organic matter of individual organs were measured on peanut seedlings during early ontogeny in order to compare fractionation during heterotrophic growth and transition to autotrophy in a species with lipid seed reserves with earlier results obtained on beans. Despite a high lipid content in peanut seeds (48%) compared with bean seeds (1.5%), the isotope composition of leaf- and root-respired CO2 as well as its changes during ontogeny were similar to already published data on bean seedlings: leaf-respired CO2 became (13)C-enriched reaching -21.5‰, while root-respired CO2 became (13)C-depleted reaching around -31‰ at the four-leaf stage. The opposite respiratory fractionation in leaves vs. roots already reported for C3 herbs was thus confirmed for peanuts. However, contrarily to beans, the peanut cotyledon-respired CO2 was markedly (13)C-enriched, and its (13)C-depletion was noted from the two-leaf stage onwards only. Carbohydrate amounts being very low in peanut seeds, this cannot be attributed solely to their use as respiratory substrate. The potential role of isotope fractionation during glyoxylate cycle and/or gluconeogenesis on the (13)C-enriched cotyledon-respired CO2 is discussed.

New Insights from Zinc and Copper Isotopic Compositions into the Sources of Atmospheric Particulate Matter from Two Major European Cities.

PubMed

Gonzalez, R Ochoa; Strekopytov, S; Amato, F; Querol, X; Reche, C; Weiss, D

2016-09-20

This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between -0.13 ± 0.09 and -0.51 ± 0.05‰ for δ(66)ZnIRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ(65)CuAE633. Copper isotope signatures similar to those of Cu sulfides and Cu/Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ(66)ZnIRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ(65)CuAE633. Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ(66)ZnIRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Heck, Philipp R.; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.;

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.; Stephan, Thomas;

Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

NASA Astrophysics Data System (ADS)

Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

2003-12-01

Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

Application of non-lethal stable isotope analysis to assess feeding patterns of juvenile pallid sturgeon Scaphirhynchus albus: a comparison of tissue types and sample preservation methods

USGS Publications Warehouse

Andvik, R.T.; VanDeHey, J.A.; Fincel, M.J.; French, William E.; Bertrand, K.N.; Chipps, Steven R.; Klumb, Robert A.; Graeb, B.D.S.

2010-01-01

Traditional techniques for stable isotope analysis (SIA) generally require sacrificing animals to collect tissue samples; this can be problematic when studying diets of endangered species such as the pallid sturgeon Scaphirhynchus albus. Our objectives were to (i) determine if pectoral fin tissue (non-lethal) could be a substitute for muscle tissue (lethal) in SIA of juvenile pallid sturgeon, and (ii) evaluate the influence of preservation techniques on stable isotope values. In the laboratory, individual juvenile pallid sturgeon were held for up to 186 day and fed chironomids, fish, or a commercially available pellet diet. Significant, positive relationships (r² ≥ 0.8) were observed between fin and muscle tissues for both δ15N and δ13C; in all samples isotopes were enriched in fins compared to muscle tissue. Chironomid and fish based diets of juvenile pallid sturgeon were distinguishable for fast growing fish (0.3 mm day−1) using stable δ15N and δ13C isotopes. Frozen and preserved fin tissue δ15N isotopes were strongly related (r2 = 0.89) but δ13C isotopes were weakly related (r2 = 0.16). Therefore, freezing is recommended for preservation of fin clips to avoid the confounding effect of enrichment by ethanol. This study demonstrates the utility of a non-lethal technique to assess time integrated food habits of juvenile pallid sturgeon and should be applicable to other threatened or endangered species.

Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

USGS Publications Warehouse

Demopoulos, Amanda W. J.; Sikkel, Paul C.

2015-01-01

Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

Isotope and trace element insights into heterogeneity of subridge mantle

NASA Astrophysics Data System (ADS)

Mallick, Soumen; Dick, Henry J. B.; Sachi-Kocher, Afi; Salters, Vincent J. M.

2014-06-01

Geochemical data for abyssal peridotites are used to determine the relationship to mid-ocean ridge basalts from several locations at ridge segments on the SW Indian Ridge (SWIR), the Mid-Cayman-Rise (MCR), and the Mid-Atlantic Ridge (MAR). Based on chemical and petrological criteria peridotites are categorized as being either dominantly impregnated with melt or being residual after recent melting. Those that are considered impregnated with melt also have isotopic compositions similar to the basalts indicating impregnation by an aggregate MORB melt. A SWIR and MCR residual peridotite Nd-isotopic compositions partly overlap the Nd-isotopic compositions of the basalts but extend to more radiogenic compositions. The differences between peridotite and basalt Nd-isotopic compositions can be explained by incorporating a low-solidus component with enriched isotopic signature in the subridge mantle: a component that is preferentially sampled by the basalts. At the MAR, peridotites and associated basalts have overlapping Nd-isotopic compositions, suggesting a more homogeneous MORB mantle. The combined chemistry and petrography indicates a complex history with several depletion and enrichment events. The MCR data indicate that a low-solidus component can be a ubiquitous component of the asthenosphere. Residual abyssal peridotites from limited geographic areas also show significant chemical variations that could be associated with initial mantle heterogeneities related to events predating the ridge-melting event. Sm-Nd model ages for possible earlier depletion events suggest these could be as old as 2.4 Ga. This article was corrected on 9 JULY 2014. See the end of the full text for details.

Pb evolution in the Martian mantle

NASA Astrophysics Data System (ADS)

Bellucci, J. J.; Nemchin, A. A.; Whitehouse, M. J.; Snape, J. F.; Bland, P.; Benedix, G. K.; Roszjar, J.

2018-03-01

The initial Pb compositions of one enriched shergottite, one intermediate shergottite, two depleted shergottites, and Nakhla have been measured by Secondary Ion Mass Spectrometry (SIMS). These values, in addition to data from previous studies using an identical analytical method performed on three enriched shergottites, ALH 84001, and Chassigny, are used to construct a unified and internally consistent model for the differentiation history of the Martian mantle and crystallization ages for Martian meteorites. The differentiation history of the shergottites and Nakhla/Chassigny are fundamentally different, which is in agreement with short-lived radiogenic isotope systematics. The initial Pb compositions of Nakhla/Chassigny are best explained by the late addition of a Pb-enriched component with a primitive, non-radiogenic composition. In contrast, the Pb isotopic compositions of the shergottite group indicate a relatively simple evolutionary history of the Martian mantle that can be modeled based on recent results from the Sm-Nd system. The shergottites have been linked to a single mantle differentiation event at 4504 Ma. Thus, the shergottite Pb isotopic model here reflects a two-stage history 1) pre-silicate differentiation (4504 Ma) and 2) post-silicate differentiation to the age of eruption (as determined by concordant radiogenic isochron ages). The μ-values (238U/204Pb) obtained for these two different stages of Pb growth are μ1 of 1.8 and a range of μ2 from 1.4-4.7, respectively. The μ1-value of 1.8 is in broad agreement with enstatite and ordinary chondrites and that proposed for proto Earth, suggesting this is the initial μ-value for inner Solar System bodies. When plotted against other source radiogenic isotopic variables (Sri, γ187Os, ε143Nd, and ε176Hf), the second stage mantle evolution range in observed mantle μ-values display excellent linear correlations (r2 > 0.85) and represent a spectrum of Martian mantle mixing-end members (depleted, intermediate, enriched).

Uranium Conversion & Enrichment

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

Karpius, Peter Joseph

2017-02-06

The isotopes of uranium that are found in nature, and hence in ‘fresh’ Yellowcake’, are not in relative proportions that are suitable for power or weapons applications. The goal of conversion then is to transform the U 3O 8 yellowcake into UF 6. Conversion and enrichment of uranium is usually required to obtain material with enough 235U to be usable as fuel in a reactor or weapon. The cost, size, and complexity of practical conversion and enrichment facilities aid in nonproliferation by design.

Isotopic fingerprint of the middle Olt River basin, Romania.

PubMed

Popescu, Raluca; Costinel, Diana; Ionete, Roxana Elena; Axente, Damian

2014-01-01

One of the most important tributaries of the Danube River in Romania, the Olt River, was characterized in its middle catchment in terms of the isotopic composition using continuous flow-isotope ratio mass spectrometry (CF-IRMS). Throughout a period of 10 months, from November 2010 to August 2011, water samples from the Olt River and its more important tributaries were collected in order to investigate the seasonal and spatial isotope patterns of the basin waters. The results revealed a significant difference between the Olt River and its tributaries, by the fact that the Olt River waters show smaller seasonal variations in the stable isotopic composition and are more depleted in (18)O and (2)H. The waters present an overall enrichment in heavy isotopes during the warm seasons.

Isotopic signals from precipitation and denitrification in nitrate in a northern hardwood forest

NASA Astrophysics Data System (ADS)

Goodale, C. L.; Wexller, S.

2012-12-01

Denitrification can represent an important term in the nitrogen budget of small catchments; however, this process varies greatly over space and time and is notoriously difficult to quantify. Measurements of the natural abundance of stable isotopes of nitrogen and oxygen in dissolved nitrate in stream- and river water can sometimes provide evidence of denitrification, particularly in large river basins or agriculturally impacted catchments. To date, however, this approach has provided little to no evidence of denitrification in catchments in temperate forests. Here, we examined d15N and d18O of nitrate in water samples collected during summer 2011 not only from streams and precipitation, but also from groundwater from the hydrologic reference watershed (W3) drained by Paradise Brook, at the Hubbard Brook Experimental Forest, in the White Mountains, New Hampshire. Despite low nitrate concentrations (< 0.5 to 8.8 uM nitrate) dual-isotopic signals of nitrate sources and nitrogen cycle processes were clearly distinguishable, including sources from atmospheric deposition, and from nitrification of atmospheric ammonium and from or soil organic nitrogen, as well as nitrate affected by soil denitrification. An atmospheric signal from nitrate in precipitation (enriched with 18O) was observed immediately following a precipitation event in mid-July contributing roughly 22% of stream nitrate export on this date. Stream samples the day following this and other storms showed this export of event nitrate to be short-lived. Hillslope piezometers showed low nitrate concentrations and high d15N- and d18O-nitrate values (averaging 12 and 18 per mil, repectively) indicating denitrification, which preferentially removes isotopically light N and O in N gases and leaves isotopically heavy nitrate behind. These samples showed a positive relationship between nitrogen and oxygen isotopic composition with a regression line slope of 0.76 (R2 = 0.68), and an isotope enrichment factor -12.7 per mil for denitrification removal of nitrate in these hillslope soils. The isotopic composition of a time series of samples from three riparian piezometers crossing Paradise Brook shows strong connections between the riparian soil water and the stream, as well as a different dominant source of nitrate in each piezometer. Repeated surveys of stream nitrate show modest positive enrichment in N and O isotopes with a slope between 18O and 15N of 0.96, indicating either in- or near-stream denitrification or mixing between stream and hillslope water bearing a stronger denitrification signal. The dual isotope approach provides detailed information on nitrogen cycling dynamics during the summer in a northern hardwood forested catchment. Together, these observations provide strong isotopic evidence for rapid rates of denitrification during summer in the soils of this small forested catchment.

Investigation into the semimagic nature of the tin isotopes through electromagnetic moments

DOE PAGES

Allmond, J. M.; Stuchbery, A. E.; Galindo-Uribarri, A.; ...

2015-10-19

A complete set of electromagnetic moments, B(E2;0 + 1 2 + 1), Q(2 + 1), and g(2 + 1), have been measured from Coulomb excitation of semi-magic 112,114,116,118,120,122,124Sn (Z = 50) on natural carbon and titanium targets. The magnitude of the B(E2) values, measured to a precision of ~4%, disagree with a recent lifetime study [Phys. Lett. B 695, 110 (2011)] that employed the Doppler- shift attenuation method. The B(E2) values show an overall enhancement compared with recent theoretical calculations and a clear asymmetry about midshell, contrary to naive expectations. A new static electric quadrupole moment, Q(2 + 1), hasmore » been measured for 114Sn. The static quadrupole moments are generally consistent with zero but reveal an enhancement near midshell; this had not been previously observed. The magnetic dipole moments are consistent with previous measurements and show a near monotonic decrease in value with neutron number. The current theory calculations fail to reproduce the electromagnetic moments of the tin isotopes. The role of 2p-2h and 4p-4h intruders, which are lowest in energy at mid shell and outside of current model spaces, needs to be investigated in the future.« less

Stages of weathering mantle formation from carbonate rocks in the light of rare earth elements (REE) and Sr-Nd-Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, Christophe; Stille, Peter

2015-04-01

Weathering mantles are widespread and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual high content of associated trace elements in weathering mantles originating from carbonate rocks, which have been poorly studied, compared to those developing on magmatic bedrocks. For instance, these enrichments can be up to five times the content of the underlying carbonate rocks. However, these studies also showed that the carbonate bedrock content only partially explains the soil enrichment for all the considered major and trace elements. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources. REE distribution patterns and Sr-Nd-Pb isotope ratios have been used because they are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments have been applied to identify mobile phases in the soil system and to yield information on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. All these geochemical informations indicate that the cambisol developing on such a typical weathering mantle ("terra fusca") has been formed through weathering of a condensed Bajocian limestone-marl facies. This facies shows compared to average world carbonates important trace element enrichments. Their trace element distribution patterns are similar to those of the soil suggesting their close genetic relationships. Sr-Nd-Pb isotope data allow to identify four principal components in the soil: a silicate-rich pool at close to the surface, a leachable REE enriched pool at the bottom of the soil profile, the limestone facies on which the weathering profile developed and an anthropogenic, atmosphere-derived component detected in the soil leachates of the uppermost soil horizon. The leachable phases are mainly secondary carbonate-bearing REE phases such as bastnaesite. The isotope data and trace element distribution patterns indicate that at least four geological and environmental events impacted the chemical and isotopical compositions of the soil system since the Cretaceous.

Distribution of stable free radicals among amino acids of isolated soy proteins.

PubMed

Lei, Qingxin; Liebold, Christopher M; Boatright, William L; Shah Jahan, M

2010-09-01

Application of deuterium sulfide to powdered isolated soy proteins (ISP) was used to quench stable free radicals and produce a single deuterium label on amino acids where free radicals reside. The deuterium labels rendered increases of isotope ratio for the specific ions of radical-bearing amino acids. Isotope ratio measurements were achieved by gas chromatography/mass spectrometry (GC/MS) analyses after the amino acids were released by acidic hydrolysis and converted to volatile derivatives with propyl chloroformate. The isotope enrichment data showed the stable free radicals were located on Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp but not on Val, Pro, Met, Phe, Lys, and His. Due to the low abundance of Ser, Thr, and Cys derivatives and the impossibility to accurately measure their isotope ratios, the radical bearing status for these amino acids remained undetermined even though their derivatives were positively identified from ISP hydrolysates. The relative isotope enrichment for radical-bearing amino acids Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp were 8.67%, 2.96%, 2.90%, 3.94%, 6.03%, 3.91%, and 21.48%, respectively. Isotope ratio increase for Tyr was also observed but further investigation revealed such increase was mainly from nonspecific deuterium-hydrogen exchange not free radical quenching. The results obtained from the present study provide important information for a better understanding of the mechanisms of free radical formation and stabilization in "dry" ISP.

The influence of microclimates and fog on stable isotope signatures used in interpretation of regional hydrology: East Maui, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Gingerich, S.B.; Tribble, G.W.

2002-01-01

Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055 m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall ??18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 3??? in ??18O and 21??? in ??D compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui ??18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000 m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240 m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area. Published by Elsevier Science B.V.

Generation and Evolution of Quaternary Magmas Beneath Tengchong: Sr-Nd-Pb-Hf Isotope and Zircon U-series Age Constraints

NASA Astrophysics Data System (ADS)

Zou, H.; Ma, M.; Fan, Q.; Xu, B.; Li, S. Q.; Zhao, Y.; King, D. T., Jr.

2017-12-01

The Tengchong volcanic field on the southeastern margin of the Tibetan Plateau represents rare Quaternary volcanic eruptions on the plateau. The Quaternary Tengchong volcanic field formed high-potassium calc-alkaline volcanic rocks that include trachybasalts, basaltic trachyandesites, trachyandesites, and dacites. Herein, we present comprehensive Nd-Sr-Pb-Hf isotopic and elemental data for trachybasalts, basaltic trachyandesites, and trachyandesites from four young Tengchong volcanoes at Maanshan, Dayingshan, Heikongshan, and Laoguipo, in order to understand their magma genesis and evolution. Nd-Sr-Pb-Hf isotopes for the primitive Tengchong magma (trachybasalts with SiO2 <52.5 wt. % and MgO >5.5% wt. %) reflect a heterogeneous enriched mantle source. High Th/U, Th/Ta, and Rb/Nb ratios and Nd-Sr-Pb-Hf isotope characteristics of the primitive magmas suggest that the enriched mantle beneath Tengchong formed as a result of subduction of clay-rich sediments, which probably came from the Indian continental plate. Partial melting of the enriched mantle was generated by deep continental subduction coupled with recent regional extension in the Tengchong area. With regard to the evolved magmas (basaltic trachyandesites and trachyandesites), good correlations between SiO2 content and the ratios 87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb, and 177Hf/176Hf strongly suggest that the combined assimilation and fractional crystallization (AFC) was an important process during magma evolution to form these basaltic trachyandesites and trachyandesites. Uranium-series zircon dating on these evolved lavas from Tengchong is used to constrain their magma evolution and residence timescales.

Amino Acid Isotopic Trophic Enrichment in Mesozooplankton: Is Alanine a Better Predictor of Protistan Grazer Steps?

NASA Astrophysics Data System (ADS)

Decima, M.; Landry, M. R.; Bradley, C. J.; Fogel, M. L.

2016-02-01

Food-web studies within marine environments are increasingly reliant upon results from compound-specific isotope analysis of amino acids (CSIA-AA). The approach is advantageous because it allows consumer trophic positions to be estimated without sampling the dynamic primary producers. The baseline signal in the source AA phenylalanine is preserved, and a constant enrichment in glutamic acid at each trophic step is assumed, regardless of consumer type or diet. However, a number of recent studies challenge the assumption of universal and invariant isotopic fractionation of glutamic acid for all trophic levels, as well as its specific applicability to the main grazers in the ocean: the protistan microzooplankton. We present results from both laboratory and field studies that further explore this issue. Experiments include six 2-stage chemostats, using two different microzooplankton-phytoplankton pairs and one copepod-phytoplankton pair, and one 3-stage experiment using a copepod-microzooplankton-phytoplankton chain. We confirm previous observations of negligible fractionation of glutamic acid in protistan consumers when nutrients are limiting. In contrast, a consistent trophic enrichment effect was observed for alanine, with increasing δ15N values by trophic level for both metazoan and protistan consumers. A re-analysis of published CSIA-AA data of zooplankton species show that an index using alanine and phenylalanine gives trophic level estimates closer to expected given current understanding of the linkages within microbial food webs. Our results examine the details of isotopic fractionation of alanine within defined food chains and generally support its potential use as a trophic level indicator that includes the protistan contribution to mesozooplankton diet.

Seasonal variation of oxygen-18 in precipitation and surface water of the Poyang Lake Basin, China.

PubMed

Hu, Chunhua; Froehlich, Klaus; Zhou, Peng; Lou, Qian; Zeng, Simiao; Zhou, Wenbin

2013-06-01

Based on the monthly δ(18)O value measured over a hydrology period in precipitation, runoff of five tributaries and the main lake of the Poyang Lake Basin, combined with hydrological and meteorological data, the characteristics of δ(18)O in precipitation (δ(18)OPPT) and runoff (δ(18)OSUR) are discussed. The δ(18)OPPT and δ(18)OSUR values range from-2.75 to-14.12 ‰ (annual mean value=-7.13 ‰ ) and from-2.30 to-8.56 ‰, respectively. The seasonal variation of δ(18)OPPT is controlled by the air mass circulation in this region, which is dominated by the Asian summer monsoon and the Siberian High during winter. The correlation between the wet seasonal averages of δ(18)OSUR in runoff of the rivers and δ(18)OPPT of precipitation at the corresponding stations shows that in the Poyang Lake catchment area the river water consists of 23% direct runoff (precipitation) and 77% base flow (shallow groundwater). This high proportion of groundwater in the river runoff points to the prevalence of wetland conditions in the Poyang Lake catchment during rainy season. Considering the oxygen isotopic composition of the main body of Poyang Lake, no isotopic enrichment relative to river inflow was found during the rainy season with maximum expansion of the lake. Thus, evaporation causing isotopic enrichment is a minor component of the lake water balance in the rainy period. During dry season, a slight isotopic enrichment has been observed, which suggests a certain evaporative loss of lake water in that period.

Affordable measurement of human total energy expenditure and body composition using one-tenth dose doubly labelled water.

PubMed

Mann, D V; Ho, C S; Critchley, L; Fok, B S P; Pang, E W H; Lam, C W K; Hjelm, N M

2007-05-01

The doubly labelled water (DLW) method is the technique of choice for measurement of free-living total energy expenditure (TEE) in humans. A major constraint on the clinical applicability of the method has been the expense of the (18)O isotope. We have used a reduced-dose (one-tenth of the currently recommended standard dose) of DLW for the measurement of TEE and body composition in nine healthy adult male volunteers. TEE measured by reduced-dose DLW was positively correlated with resting energy expenditure measured by metabolic cart (r=0.87, P<0.01). Isotope-derived fat mass and body mass index were strongly correlated (r=0.86, P<0.01). In four subjects in whom we performed a complementary evaluation using standard-dose isotope enrichment, the TEE measurements were satisfactorily comparable (mean+/-s.d.: reduced dose 2586+/-155 kcal/day vs standard dose 2843+/-321 kcal/day; mean difference 257+/-265 kcal/day). These data indicate that DLW measurements of human energy expenditure and body composition can be performed at a substantially reduced dose (and cost) of isotope enrichment than is currently employed.

The meteoritic record of presolar and early solar system organic chemistry. [Abstract only

NASA Technical Reports Server (NTRS)

Cronin, John R.; Pizzarello, Sandra

1994-01-01

Carbon, hydrogen, and nitrogen isotopic analyses of various classes of organic compounds done in collaboration with Epstein and Krishnamurthy (Caltech) have shown these compounds to be enriched to varying degrees in the heavier isotopes. These results, in particular the large deuterium enrichments, have been interpreted as indicating an interstellar origin for the meteorite compounds or their precursors. Such isotopic fractionations, of hydrogen especially, are characteristic of low temperature ion-molecule reactions in cold interstellar clouds. There is also evidence from the large corresponding suites of alpha-amino and alpha-hydroxy acids found in meteorites suggesting that aqueous phase chemistry on the meteorite parent body played an important role in the formation of these compounds. These data support the hypothesis that interstellar compounds survived in the solar nebula at a radial distance corresponding to the asteroid belt, were incorporated into the parent body in icy, volatile-rich, planetesinals, and underwent further reactions during a period of aqueous activity within the early parent body to give the present suite of meteorite compounds. This formation hypothesis will be discussed and the results of recent isotopic and molecular analyses bearing on it will be presented.

Isotopic separation of snowmelt runoff during an artificial rain-on-snow event

NASA Astrophysics Data System (ADS)

Juras, Roman; Pavlasek, Jirka; Šanda, Martin; Jankovec, Jakub; Linda, Miloslav

2013-04-01

Rain-on-snow events are common phenomenon in the climate conditions of central Europe, mainly during the spring snowmelt period. These events can cause serious floods in areas with seasonal snow. The snowpack hit by rain is able to store a fraction of rain water, but runoff caused by additional snowmelt also increases. Assessment of the rainwater ratio contributing to the outflow from the snowpack is therefore critical for discharge modelling. A rainfall simulator and water enriched by deuterium were used for the study of rainwater behaviour during an artificial rain-on-snow event. An area of 1 m2 of the snow sample, which was 1.2 m deep, consisting of ripped coarse-grained snow, was sprayed during the experiment with deuterium enriched water. The outflow from the snowpack was measured and samples of outflow water were collected. The isotopic content of deuterium was further analyzed from these samples by means of laser spectroscopy for the purpose of hydrograph separation. The concentration of deuterium in snow before and after the experiment was also investigated. The deuterium enriched water above the natural concentration of deuterium in snowpack was detected in the outflow in 7th minute from start of spraying, but the significant increase of deuterium concentration in outflow was observed in 19th minute. The isotopic hydrograph separation estimated, that deuterium enriched rainwater became the major part (> 50% volumetric) of the outflow in 28th minute. The culmination of the outflow (1.23 l min-1) as well as deuterium enriched rainwater fraction (63.5%) in it occurred in 63th minute, i.e. right after the end of spraying. In total, 72.7 l of deuterium enriched water was sprayed on the snowpack in 62 minutes. Total volume of outflow (after 12.3 hours) water was 97.4 l, which contained 48.3 l of deuterium enriched water (i.e. 49.6 %) and 49.1 l (50.4 %) of the melted snowpack. The volume of 24.4 l of deuterium enriched spray-water was stored in the snowpack. The increased total output v. input of the water volume was caused by the warmer spray-water induced snowmelt also connecting separated liquid layers in the snowpack within the process of infiltration and drainage. Key words: deuterium tracer, rainfall simulator, snowmelt

Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data

PubMed Central

Chakraborty, Subrata; Muskatel, B. H.; Jackson, Teresa L.; Ahmed, Musahid; Levine, R. D.; Thiemens, Mark H.

2014-01-01

Nitrogen isotopic distributions in the solar system extend across an enormous range, from −400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ15N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ15N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula. PMID:25267643

Oxygen reservoirs in the early solar nebula inferred from an Allende CAI.

PubMed

Young, E D; Russell, S S

1998-10-16

Ultraviolet laser microprobe analyses of a calcium-aluminum-rich inclusion (CAI) from the Allende meteorite suggest that a line with a slope of exactly 1.00 on a plot of delta (17)O against delta (18)O represents the primitive oxygen isotope reservoir of the early solar nebula. Most meteorites are enriched in (17)O and (18)O relative to this line, and their oxygen isotope ratios can be explained by mass fractionation or isotope exchange initiating from the primitive reservoir. These data establish a link between the oxygen isotopic composition of the abundant ordinary chondrites and the primitive (16)O-rich component of CAIs.

Oxygen reservoirs in the early solar nebula inferred from an allende CAI

PubMed

Young; Russell

1998-10-16

Ultraviolet laser microprobe analyses of a calcium-aluminum-rich inclusion (CAI) from the Allende meteorite suggest that a line with a slope of exactly 1.00 on a plot of delta17O against delta18O represents the primitive oxygen isotope reservoir of the early solar nebula. Most meteorites are enriched in 17O and 18O relative to this line, and their oxygen isotope ratios can be explained by mass fractionation or isotope exchange initiating from the primitive reservoir. These data establish a link between the oxygen isotopic composition of the abundant ordinary chondrites and the primitive 16O-rich component of CAIs.

Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

NASA Astrophysics Data System (ADS)

Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

2014-07-01

In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

Isotopic Discrimination During Leaf Litter Decomposition

NASA Astrophysics Data System (ADS)

Ngao, J.; Rubino, M.

2006-12-01

Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to implement an advanced laser spectrometry technology to measure the isotopic composition in respired CO2. The laser spectrometer will be used to investigate the isotopic discrimination during soil respiration, in laboratory and field studies.

The influence of low latitude forcing on European Ice sheet dynamics

NASA Astrophysics Data System (ADS)

Kaboth, Stefanie; Bahr, André; Lourens, Lucas J.

2017-04-01

Distinct mid-glacial δ18O enrichment events found at Site U1386 in the Gulf of Cadiz during Marine Isotope Stages 6 and 8 represent a striking feature absent in most deep-sea benthic δ18O records studied worldwide. These δ18O enrichment events are closely related to periods of maximum precession and aligned with previous findings from the Mediterranean and Red Seas. Here we present paired planktic and benthic stable isotope (δ18O and δ13C) and Mg/Ca-based temperature records of Site U1386 of the last 300.000 years. Our results show that these δ18O enrichment events are recorded in both subsurface and bottom water masses and pre-date the largest cooling events along the Iberian Margin and associated European sourced meltwater pulses of the Drenthe and Fuhne major ice-sheet advances, suggesting that they instead correspond to periods of maximum ice volume extend in Europe.

Fuel preparation for use in the production of medical isotopes

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

Policke, Timothy A.; Aase, Scott B.; Stagg, William R.

The present invention relates generally to the field of medical isotope production by fission of uranium-235 and the fuel utilized therein (e.g., the production of suitable Low Enriched Uranium (LEU is uranium having 20 weight percent or less uranium-235) fuel for medical isotope production) and, in particular to a method for producing LEU fuel and a LEU fuel product that is suitable for use in the production of medical isotopes. In one embodiment, the LEU fuel of the present invention is designed to be utilized in an Aqueous Homogeneous Reactor (AHR) for the production of various medical isotopes including, butmore » not limited to, molybdenum-99, cesium-137, iodine-131, strontium-89, xenon-133 and yttrium-90.« less

Isotopic separation of D.sub.2 O from H.sub.2 O using ruthenium adsorbent

DOEpatents

Thiel, Patricia A.

1990-04-10

A method of enrichment of D.sub.2 O in solutions of D.sub.2 O in H.sub.2 O by contacting said solutions in the steam phase with hexagonal crystalline to produce enriched D.sub.2 O. The passages may be repeated to achieve a desired amount of D.sub.2 O.

The effect of nitrogen loading on a brackish estuarine faunal community: A stable isotope approach

USGS Publications Warehouse

Keats, R.A.; Osher, L.J.; Neckles, H.A.

2004-01-01

Coastal ecosystems worldwide face increased nutrient enrichment from shoreline and watershed development and atmospheric pollution. We investigated the response of the faunal community of a small microtidal estuary dominated by Ruppia maritima (widgeon grass) in Maine, United States, to increased nitrogen loading using an in situ mesocosm enrichment experiment. Community response was characterized by assessing quantitative shifts in macroin-vertebrate community composition and identifying changes in food web structure using stable carbon and nitrogen isotope ratios of producers and consumers. The community was dominated by brackish water invertebrates including midge larvae, oligochaetes, damselfly larvae, amphipods, and ostracods. Experimental nutrient additions resulted in significantly lower densities of herbivorous chironomids and predatory damselflies and greater densities of deposit feeding oligochaetes. Grazing midge larvae (Chironomidae: Dicrotendipes, Cricotopus) consumed epiphytic algae under both natural and enriched conditions. Deposit feeding Chironomus was dependent on allochthonous sources of detritus under natural conditions and exhibited a shift to autochthonous sources of detritus under enriched conditions. Predatory Enallagma primarily consumed grazing chironomids under all but the highest loading conditions. Experimental nutrient loading resulted in an increase in generalist deposit feeders dependent on autochthonous sources of detritus.

Lunar and Planetary Science XXXVI, Part 10

NASA Technical Reports Server (NTRS)

2005-01-01

The Problem of Incomplete Mixing of Interstellar Components in the Solar Nebula: Very High Precision Isotopic Measurements with Isoprobes P and T. Finally: Presolar Graphite Grains Identified in Orgueil. Basaltic Ring Structures as an Analog for Ring Features in Athabasca Valles, Mars. Experimental Studies of the Water Sorption Properties of Mars-Relevant Porous Minerals and Sulfates. Silicon Isotope Ratio Variations in CAI Evaporation Residues Measured by Laser Ablation Multicollector ICPMS. Crater Count Chronology and Timing of Ridged Plains Emplacement at Schiaparelli Basin, Mars. Martian Valley Networks and Associated Fluvial Features as Seen by the Mars Express High Resolution Stereo Camera (HRSC). Fast-Turnoff Transient Electromagnetic (TEM) Field Study at the Mars Analog Site of Rio Tinto, Spain. Time Domain Electromagnetics for Mapping Mineralized and Deep Groundwater in Mars Analog Environments. Mineralogical and Seismological Models of the Lunar Mantle. Photometric Observations of Soils and Rocks at the Mars Exploration Rover Landing Sites. Thermal Infrared Spectral Deconvolution of Experimentally Shocked Basaltic Rocks Using Experimentally Shocked Plagioclase Endmembers.

High latitude hydrological changes during the Eocene Thermal Maximum 2

NASA Astrophysics Data System (ADS)

Krishnan, Srinath; Pagani, Mark; Huber, Matthew; Sluijs, Appy

2014-10-01

The Eocene hyperthermals, including the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2), represent extreme global warming events ∼56 and 54 million years ago associated with rapid increases in atmospheric greenhouse gas concentrations. An initial study on PETM characteristics in the Arctic region argued for intensification of the hydrological cycle and a substantial increase in poleward moisture transport during global warming based on compound-specific carbon and hydrogen isotopic (2H/1H) records from sedimentary leaf-wax lipids. In this study, we apply this isotopic and hydrological approach on sediments deposited during ETM2 from the Lomonosov Ridge (Integrated Ocean Drilling Program Expedition 302). Our results show similar 2H/1H changes during ETM2 as during the PETM, with a period of 2H-enrichment (∼ 20 ‰) relative to ;pre-event; values just prior to the negative carbon isotope shift (CIE) that is often taken as the onset of the hyperthermal, and more negative lipid δ2H values (∼ - 15 ‰) during peak warming. Notably, lipid 2H-enrichment at the base of the event is coeval with colder TEX86H temperatures. If 2H/1H values of leaf waxes primarily reflect the hydrogen isotopic composition of precipitation, the observed local relationship between temperature and 2H/1H values for the body of ETM2 is precisely the opposite of what would be predicted using a simple Rayleigh isotope distillation model, assuming a meridional vapor trajectory and a reduction in equator-pole temperature gradients. Overall, a negative correlation exists between the average chain length of n-alkanes and 2H/1H suggesting that local changes in ecology could have impacted the hydrogen isotopic compositions of leaf waxes. The negative correlation falls across three separate intervals - the base of the event, the initial CIE, and during the H2 hyperthermal (of which the assignment is not fully certain). Three possible mechanisms potentially explain 2H-enriched signals at the base of the event, including (1) intense local drying and cooling leading to evaporative 2H-enrichment; (2) changes in frequency/intensity of storm events and its impact on high latitude amount effects; and (3) changes in low-latitude temperatures. Evidence for hydrological shifts at the base of both hyperthermals suggests that hydrological change or the factors promoting hydrological change played a role in triggering the release of greenhouse gases. Generation of similar high-resolution isotopic- and temperature records at other latitudes is crucial for understanding the causal links between temperature and hydrological changes and may help constrain the source and mechanism of carbon release that triggered the early Eocene hyperthermals.

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

2016-01-01

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (dD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (dD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

Assessment of marine-derived nutrients in the Copper River Delta, Alaska, using natural abundance of the stable isotopes of nitrogen, sulfur, and carbon

USGS Publications Warehouse

Kline, Thomas C.; Woody, Carol Ann; Bishop, Mary Anne; Powers, Sean P.; Knudsen, E. Eric

2007-01-01

We performed nitrogen, sulfur, and carbon stable isotope analysis (SIA) on maturing and juvenile anadromous sockeye and coho salmon, and periphyton in two Copper River delta watersheds of Alaska to trace salmonderived nutrients during 2003–2004. Maturing salmon were isotopically enriched relative to alternate freshwater N, S, and C sources as expected, with differences consistent with species trophic level differences, and minor system, sex, and year-to-year differences, enabling use of SIA to trace these salmon-derived nutrients. Periphyton naturally colonized, incubated, and collected using Wildco Periphtyon Samplers in and near spawning sites was 34S- and 15N-enriched, as expected, and at all freshwater sites was 13C-depleted. At nonspawning and coho-only sites, periphyton 34S and 15N was generally low. However, 34S was low enough at some sites to be suggestive of sulfate reduction, complicating the use of S isotopes. Juvenile salmon SIA ranged in values consistent with using production derived from re-mineralization as well as direct utilization, but only by a minority fraction of coho salmon. Dependency on salmon-derived nutrients ranged from relatively high to relatively low, suggesting a space-limited system. No one particular isotope was found to be superior for determining the relative importance of salmon-derived nutrients.

Deposition Profile Analysis from DIII-D Metal Rings Campaign Outer-Midplane Collector Probe Diagnostic and Utilization of Enriched Isotopic Tungsten Tracer Particles

NASA Astrophysics Data System (ADS)

Donovan, D. C.; Duran, J.; Zamperini, S.; Lee, S.; Unterberg, E. A.; Wampler, W. R.; Rudakov, D. L.; Elder, D.; Stangeby, P. C.; Abrams, T.

2017-10-01

The DIII-D Metal Rings Campaign used isotopically-enriched, W-coated divertor tiles coupled with dual-facing midplane collector probes (CPs) in the far Scrape-off Layer (SOL). Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) results are presented characterizing the isotopic ratios of deposited W on the CPs and which give quantitative information on the transport of W from specific poloidal locations within the lower outer divertor region having different isotopically-marked tiles. Rutherford Backscattering Spectrometry (RBS) of these CPs has provided areal densities of elemental W content. These resultant W deposition profiles were compared with DIVIMP modelling of the far-SOL to better understand impurity transport in the edge plasma. CPs were exposed for 37 distinct operating configurations (L-mode/H-mode, forward/reverse Bt, strikepoint position). Radial decay lengths (RDL) between 5 and 50 mm were observed with consistently narrower RDL and higher peak W content on the side of the probes connected along field lines to the inner divertor, indicating a concentration of W in the upstream plasma. Correlations are discussed between peak W content, RDL, and isotopic profiles on the CPs over a wide range of conditions. Work supported by US DOE under DE-AC05-00OR22725, DE-FG02-07ER54917, DE-FC02-04ER54698, DE-NA0003525.

Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat.

PubMed

Goode, Laurel K; Erhardt, Erik B; Santiago, Louis S; Allen, Michael F

2010-07-01

We studied C stable isotopic composition (delta(13)C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C(3) photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in (13)C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue delta(13)C differed by species and by forest type, with values from open-canopied wetlands more enriched in (13)C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C(3) pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C(3) pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis.

Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat

PubMed Central

Erhardt, Erik B.; Santiago, Louis S.; Allen, Michael F.

2010-01-01

We studied C stable isotopic composition (δ13C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C3 photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in 13C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue δ13C differed by species and by forest type, with values from open-canopied wetlands more enriched in 13C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C3 pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C3 pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis. PMID:20155286

On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

PubMed

Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

2014-12-03

We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. Copyright © 2014 Elsevier B.V. All rights reserved.

Pb concentrations and isotopic record preserved in northwest Greenland snow.

PubMed

Kang, Jung-Ho; Hwang, Heejin; Han, Changhee; Hur, Soon Do; Kim, Seong-Joong; Hong, Sungmin

2017-11-01

We present high-resolution lead (Pb) concentrations and isotopic ratios from a northwest Greenland snow pit covering a six-year period between 2003 and 2009. Pb concentrations ranged widely from 2.7 pg g -1 to 97.3 pg g -1 , with a mean concentration of 21.6 pg g -1 . These values are higher than those recorded for the pre-industrial period. Pb concentrations exhibit seasonal spikes in winter-spring layers. Crustal Pb enrichment factors (EF) suggest that the northwest Greenland snow pit is highly enriched with Pb of predominantly anthropogenic origin. The 206 Pb/ 207 Pb ratios ranged from 1.144 to 1.169 with a mean value of 1.156, which fall between less radiogenic Eurasian-type and more radiogenic Canadian-type signatures. This result suggests that several potential source areas of Pb impact on northwest Greenland. Abrupt changes in Pb concentrations and Pb isotope ratios were observed and related to seasonal shifts in source regions of aerosol transport. The 206 Pb/ 207 Pb isotope ratio increased gradually between 2003 and 2009. The similarity of the three-isotope plot ( 206 Pb/ 207 Pb versus 208 Pb/ 207 Pb) between some of our samples and Chinese urban aerosols suggests a steadily increasing contribution of Chinese Pb to northwest Greenland snow. Copyright © 2017. Published by Elsevier Ltd.

Sulfur and Oxygen Isotopic Analysis of a Cosmic Symplectite from a Comet Wild 2 Stardust Terminal Particle

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Berger, E. L.; Nakamura-Messenger, K.; Messenger, S.

2015-01-01

Introduction: Analyses of comet 81P/Wild 2 samples re-turned from the Stardust mission have uncovered surprising simi-larities to meteoritic material, including the identification of inner solar system grains [1-3]. The TEM characterization of terminal particle (TP) 4 from Stardust track #147 revealed an assemblage consisting of symplectically intergrown pentlandite and nanocrys-talline maghemite coexisting with high-Ca pyroxene [4]. Mineral-ogically similar cosmic symplectites (COS) containing pentlandite and magnetite in the primitive Acfer 094 meteorite are highly de-pleted in 16O (?17O, ?18O 180 per mille) [5-7]. This isotopic signature is proposed to record alteration with primordial solar nebula water. Conversely, the normal O isotopic composition of the Stardust COS indicates alteration by a different aqueous reservoir, perhaps on the comet [8]. In this study, we analyzed the Wild 2 COS for S isotopes to further constrain its origin. Experimental: Thin sections of TP4 (12 ?m) were produced and their mineralogy was thoroughly characterized by TEM. Two of the sections were analyzed for O isotopes by isotopic imaging in the JSC NanoSIMS 50L. The sample in one of the slices was completely consumed. The remaining material in the adjacent slice was analyzed simultaneously for 16O, 32S, 33S, 34S, and 56Fe16O in electron multipliers using a Cs+ primary ion beam. Quasi-simulta-neous arrival (QSA) can have a significant effect on S isotopic ra-tios when using electron multipliers, resulting in undercounting of 32S [9]. Canyon Diablo troilite (CDT) was measured numerous times to deduce a correction factor for QSA and ensure measure-ment reproducibility. Isotopic ratios are reported relative to CDT. Results and Discussion: The Wild 2 COS is enriched in the heavy S isotopes relative to CDT (?33S = 6.5 +/- 1.6 per mille; ?34S = 5.1 +/- 0.7 per mille; 1?). The degree of 33S enrichment indicates mass-inde-pendent fractionation (MIF) with ?33S = 3.9 +/- 1.7 per mille. MIF of S has been observed in some chondrules (?33S up to 0.11per mille) [10], but this effect has not been identified in sulfides from carbonaceous chondrites [11] or IDPs [12]. S isotopic analysis of Stardust impact craters also did not reveal MIF or anomalies, save for one potential 32S-rich presolar sulfide [13]. Measurement errors on these impact craters were much larger than those in this study, however. MIF of S has been proposed to result from heterogeneities in the solar neb-ula from nucleosynthetic components [14] or photochemical irra-diation of solar nebula gas [10]. Presolar SiC grains are observed to have 32S enrichments [15, 16] contrary to the S isotopic compo-sition of the cometary COS. The S isotopic composition more likely reflects irradiation of nebular gas.

Evidence from mantle xenoliths for lithosphere removal beneath the central Rio Grande Rift

NASA Astrophysics Data System (ADS)

Byerly, Benjamin L.; Lassiter, John C.

2012-11-01

Seismic tomography beneath the Central Rio Grande Rift (RGR) at ˜34°N shows a low P and S wave velocity zone in the mantle that extends up the base of the Moho. This low-velocity region has been interpreted by (Gao et al., 2004) to be the result of convective removal of a portion of the once >100 km thick Proterozoic lithosphere. The amount of extension in the central RGR is thought to be low (˜25%) and thus cannot account for the amount of lithosphere thinning suggested by seismic tomography. We measured whole rock and mineral major element, trace element, and isotopic compositions of spinel-peridotite xenoliths erupted along the central axis of the rift (Elephant Butte) and the eastern margin of the Colorado Plateau (Cerro Chato) to determine their depth of origin and mantle provenance and to test the delamination hypothesis. If lithosphere removal has not occurred and the low P and S wave velocities are instead the result of hydration or melt infiltration in the lithosphere, then xenoliths erupted on the rift axis should have geochemical compositions similar to Proterozoic sub-continental lithospheric mantle (SCLM). At Cerro Chato, on the margin of the Colorado Plateau, xenoliths were derived from ˜60 km depth and have geochemical signatures similar to Proterozoic sub-continental lithospheric mantle (e.g. refractory major element compositions, LREE-enrichment, enriched Sr and Nd isotopes, unradiogenic Os isotopes). At Elephant Butte, along the central rift axis, two distinct groups of xenoliths are present. The majority of xenoliths from Elephant Butte are LREE-depleted and have fertile major element compositions. Additionally, these xenoliths have isotopic signatures similar to the range for DMM (e.g. 87Sr/86Sr ranging from 0.7018 to 0.7023, ɛNd ranging from 7 to 21, and 187Os/188Os ranging from 0.122 to 0.130). We interpret this group of xenoliths to be derived from asthenospheric mantle. A less-abundant group of xenoliths at Elephant Butte are LREE enriched, have refractory major element compositions, enriched Sr, Nd, and Pb isotopes, and unradiogenic Os isotopes. These are characteristic of Proterozoic SCLM. Both groups of xenoliths from Elephant Butte are derived from ˜45 km depth. We interpret the suite of xenoliths at Elephant Butte to have sampled what was recently the base of the Proterozoic SCLM. We conclude that a portion of the mantle lithosphere has been removed which allowed modern convecting mantle (DMM) to be emplaced at the base of the pre-existing SCLM.

Large volume recycling of oceanic lithosphere over short time scales: geochemical constraints from the Caribbean Large Igneous Province

NASA Astrophysics Data System (ADS)

Hauff, F.; Hoernle, K.; Tilton, G.; Graham, D. W.; Kerr, A. C.

2000-01-01

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ˜3×10 6 km 2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96±0.16, n=64 out of 79 samples, 2σ) and initial Nd-Pb isotopic compositions (e.g. 143Nd/ 144Nd in=0.51291±3, ɛNdi=7.3±0.6, 206Pb/ 204Pb in=18.86±0.12, n=54 out of 66, 2σ). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/ 4He in olivines of enriched picrites at Quepos are ˜12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been ≤500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

Ion probe measurements of carbon and nitrogen in iron meteorites

NASA Astrophysics Data System (ADS)

Sugiura, Naoji

1998-05-01

Carbon and nitrogen distributions in iron meteorites, their concentrations in various phases, and their isotopic compositions in certain phases were measured by secondary ion mass spectrometry (SIMS). Taenite (and its decomposition products) is the main carrier of carbon except for IAB irons where graphite and/or carbide (cohenite) may be the main carrier. Taenite is also the main carrier of nitrogen in most iron meteorites unless nitrides (carlsbergite CrN or roaldite (Fe,Ni)4N) are present. Carbon and nitrogen distributions in taenite are well correlated, unless carbides and/or nitrides are exsolved. There seem to be three types of C and N distributions within taenite. 1) These elements are enriched at the center of taenite (convex type). 2) They are enriched at the edge of taenite (concave type). 3) They are enriched near but some distance away from the edge of taenite (complex type). The case 1) is explained as equilibrium distribution of C and N in Fe-Ni alloy with M- shape nickel concentration profile. The case 2) seems to be best explained as diffusion controlled C and N distributions. In the case 3), the interior of taenite has been transformed to the a phase (kamacite or martensite). C and N were expelled from the a phase and enriched near the inner border of the remaining g phase. Such differences in the C and N distributions in taenite may reflect different cooling rates of iron meteorites. Nitrogen concentrations in taenite are quite high approaching 1 wt.% in some irons. Nitride (carlsbergite and roaldite) is present in meteorites with high nitrogen concentrations in taenite, suggesting that the nitride was formed due to supersaturation of the metallic phases with nitrogen. The same tendency is generally observed for carbon, i.e. high C concentrations in taenite correlate with the presence of carbide and/or graphite. Concentrations of C and N in kamacite are generally below detection limits. Isotopic compositions of C and N in taenite can be measured with a precision of several permil. Isotopic analysis in kamacite in most iron meteorites is not possible, because of the low concentrations. The C isotopic compositions seem to be somewhat fractionated among various phases, reflecting closure of carbon transport at low temperatures. A remarkable isotopic anomaly was observed for the Mundrabilla (IIICD anomalous) meteorite. Nitrogen isotopic compositions of taenite measured by SIMS agree very well with those of the bulk samples measured by conventional mass-spectrometry.

Investigation of Isotopically Tailored Boron in Advanced Fission and Fusion Reactor Systems.

NASA Astrophysics Data System (ADS)

Domaszek, Gerald Raymond

This research examines the use of B^ {11}, in the form of metallic boron and boron carbide, as a moderating and reflecting material. An examination of the neutronic characteristics of the B ^{11} isotope of boron has revealed that B^{11} has neutron scattering and absorption cross sections favorably comparable to those of Be^9 and C^ {12}. Preliminary analysis of the neutronics of B ^{11} were performed by conducting one dimensional transport calculations on an infinite slab of varying thickness. Beryllium is the best of the three materials in reflecting neutrons due primarily to the contribution from (n,2n) reactions. Tailored neutron energy beam transmission experiments were carried out to experimentally verify the predicted neutronic characteristics of B^{11 }. To further examine the neutron moderating and reflecting characteristics of B^{11 }, the energy dependent neutron flux was measured as a function of position in an exponential pile constructed of B_4C isotopically enriched to 98.5 percent B^{11}. After the experimental verification of the neutronic behavior of B^{11}, further design studies were conducted using metallic boron and boron carbide enriched in the B^{11 } isotope. The use of materials isotopically enriched in B^{11} as a liner in the first wall/blanket of a magnetic confinement fusion reactor demonstrated acceptable tritium regeneration in the lithium blanket. Analysis of the effect of contaminant levels of B^{10} showed that B^{10} contents of less than 1 percent in metallic boron produced negligible adverse effects on the tritium breeding. A comparison of the effectiveness of graphite and B^{11}_4C when used as moderators in a reactor fueled with natural uranium has shown that the maximum k_infty for a given fuel rod design is approximately the same for both materials. Approximately half the volume of the moderator is required when B^{11 }_4C is substituted for graphite to obtain essentially the same K_infty . An analysis of the effectiveness of various materials as reflector control elements for a compact space reactor has shown that B^{11} is neutronically superior to graphite in these applications. Metallic boron and boron carbide isotopically enriched in B^{11} have been demonstrated to be neutronically acceptable for varied applications in advanced reactor systems. B^ {11} has been shown to be superior in performance to graphite. While only somewhat inferior to beryllium as neutron multipliers, B^ {11} and B^{11} _4C have safety, supply and cost advantage over beryllium. (Abstract shortened with permission of author.).

Paleohydrologic change across the Paleocene-Eocene Thermal Maximum, Bighorn Basin, WY

NASA Astrophysics Data System (ADS)

Baczynski, A. A.; McInerney, F. A.; Wing, S. L.; Kraus, M. J.

2013-12-01

One of the uncertainties in accurately predicting future climate change involves how the hydrologic cycle will respond to increasing pCO2 and temperature. Quantifying the relationship between carbon cycle perturbations and the hydrologic cycle in the geologic past is crucial to understanding and accurately modeling how anthropogenic carbon emissions will affect future changes in the hydrologic cycle. Records of paleohydrologic response to global warming in the geologic past are rare, particularly for continental interiors, where climate model projections of precipitation are highly uncertain. Here we examine hydrogen isotope ratios of leaf waxes as a tool for reconstructing paleohydrologic change in the continental interior of North America across the Paleocene-Eocene Thermal Maximum (PETM), an abrupt, transient episode of extreme global warming ~56 Ma. New hydrogen isotope measurements of leaf-wax n-alkanes from the southeastern Bighorn Basin, Wyoming record two positive shifts during the PETM. n-Alkane δD values first shift to more positive values just after the onset of the carbon isotope excursion and then again higher up in the body of the carbon isotope excursion, with a return to slightly more negative δD values in between. Paleobotanical, paleopedologic, and isotope data from the same field area have suggested that the Bighorn Basin may have experienced a drier or more seasonally dry climate during the PETM. Mean annual precipitation estimates based on paleosol major oxides, soil wetness assessed using the soil morphology index, and an aridity proxy based on differences in δ18O values of tooth enamel in aridity-sensitive and aridity-insensitive mammals each independently suggest a potential two-phase drying within the PETM interval. Similarly, the hydrogen isotope record could reflect two periods of drying, with a return to slightly wetter conditions in between. However, leaf-wax hydrogen isotope ratios reflect not only source water hydrogen isotope values but also deuterium-enrichment resulting from soil evaporation and transpiration. Interpretation of hydrogen isotope records requires consideration of both of these factors. To examine the potential roles of changes in source water isotopic composition and transpirational D-enrichment, we compare the hydrogen isotope ratios of leaf waxes with the oxygen isotope ratios of tooth enamel from Coryphodon, a large herbivore and an obligate drinker. The Coryphodon tooth enamel δ18O record enables us to constrain shifts in surface water isotope values. Relative humidity of paleoenvironments can then be explored using a modified Craig-Gordon model for transpirational D-enrichment. Preliminary calculations suggest that relative humidity increased during the PETM, contrary to the drying suggested by all other aridity proxies. One possibility is that leaf waxes record only the relative humidity at the time of leaf formation. Therefore, the n-alkane δD record could reflect an increase in seasonality of precipitation, with greater relative humidity during the early growing season. To evaluate the validity of this approach, we will systematically examine the assumptions involved in using hydrogen isotope ratios of leaf waxes as a paleoaridity index to evaluate paleohydrologic changes in the Bighorn Basin during the PETM.

Tracing subduction zone fluid-rock interactions using trace element and Mg-Sr-Nd isotopes

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Teng, Fang-Zhen; Li, Shu-Guang; Zhang, Li-Fei; Du, Jin-Xue; He, Yong-Sheng; Niu, Yaoling

2017-10-01

Slab-derived fluids play a key role in mass transfer and elemental/isotopic exchanges in subduction zones. The exhumation of deeply subducted crust is achieved via a subduction channel where fluids from various sources are abundant, and thus the chemical/isotopic compositions of these rocks could have been modified by subduction-zone fluid-rock interactions. Here, we investigate the Mg isotopic systematics of eclogites from southwestern Tianshan, in conjunction with major/trace element and Sr-Nd isotopes, to characterize the source and nature of fluids and to decipher how fluid-rock interactions in subduction channel might influence the Mg isotopic systematics of exhumed eclogites. The eclogites have high LILEs (especially Ba) and Pb, high initial 87Sr/86Sr (up to 0.7117; higher than that of coeval seawater), and varying Ni and Co (mostly lower than those of oceanic basalts), suggesting that these eclogites have interacted with metamorphic fluids mainly released from subducted sediments, with minor contributions from altered oceanic crust or altered abyssal peridotites. The positive correlation between 87Sr/86Sr and Pb* (an index of Pb enrichment; Pb* = 2*PbN/[CeN + PrN]), and the decoupling relationships and bidirectional patterns in 87Sr/86Sr-Rb/Sr, Pb*-Rb/Sr and Pb*-Ba/Pb spaces imply the presence of two compositionally different components for the fluids: one enriched in LILEs, and the other enriched in Pb and 87Sr/86Sr. The systematically heavier Mg isotopic compositions (δ26Mg = - 0.37 to + 0.26) relative to oceanic basalts (- 0.25 ± 0.07) and the roughly negative correlation of δ26Mg with MgO for the southwestern Tianshan eclogites, cannot be explained by inheritance of Mg isotopic signatures from ancient seafloor alteration or prograde metamorphism. Instead, the signatures are most likely produced by fluid-rock interactions during the exhumation of eclogites. The high Rb/Sr and Ba/Pb but low Pb* eclogites generally have high bulk-rock δ26Mg values, whereas high Pb* and 87Sr/86Sr eclogites have mantle-like δ26Mg values, suggesting that the two fluid components have diverse influences on the Mg isotopic systematics of these eclogites. The LILE-rich fluid component, possibly derived from mica-group minerals, contains a considerable amount of isotopically heavy Mg that has shifted the δ26Mg of the eclogites towards higher values. By contrast, the 87Sr/86Sr- and Pb-rich fluid component, most likely released from epidote-group minerals in metasediments, has little Mg so as not to modify the Mg isotopic composition of the eclogites. In addition, the influence of talc-derived fluid might be evident in a very few eclogites that have low Rb/Sr and Ba/Pb but slightly heavier Mg isotopic compositions. These findings represent an important step toward a broad understanding of the Mg isotope geochemistry in subduction zones, and contributing to understanding why island arc basalts have averagely heavier Mg isotopic compositions than the normal mantle.

Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon

NASA Astrophysics Data System (ADS)

Russe, K.; Valkiers, S.; Taylor, P. D. P.

2004-07-01

Synthetic isotope mixtures for the calibration of carbon isotope amount ratio measurements have been prepared by mixing carbon tetrafluoride highly enriched in 13C with carbon tetrafluoride depleted in 13C. Mixing procedures based on volumetry and gravimetry are described. The mixtures served as primary measurement standards for the calibration of isotope amount ratio measurements of the Isotopic Reference Materials PEF1, NBS22 and USGS24. Thus SI-traceable measurements of absolute carbon isotope amount ratios have been performed for the first time without any hypothesis needed for a correction of oxygen isotope abundances, such as is the case for measurements on carbon dioxide. As a result, "absolute" carbon isotope amount ratios determined via carbon tetrafluoride have smaller uncertainties than those published for carbon dioxide. From the measurements of the Reference Materials concerned, the absolute carbon isotope amount ratio of Vienna Pee Dee Belemnite (VPDB)--the hypothetical material upon which the scale for relative carbon isotope ratio measurements is based--was calculated to be R13(VPDB) = (11 101 +/- 16) × 10-6.

Large-scale shell-model calculations for 32-39P isotopes

NASA Astrophysics Data System (ADS)

Srivastava, P. C.; Hirsch, J. G.; Ermamatov, M. J.; Kota, V. K. B.

2012-10-01

In this work, the structure of 32-39P isotopes is described in the framework of stateof-the-art large-scale shell-model calculations, employing the code ANTOINE with three modern effective interactions: SDPF-U, SDPF-NR and the extended pairing plus quadrupole-quadrupoletype forces with inclusion of monopole interaction (EPQQM). Protons are restricted to fill the sd shell, while neutrons are active in the sd - pf valence space. Results for positive and negative level energies and electromagnetic observables are compared with the available experimental data.

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

PubMed

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

2016-04-19

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

Ba isotopic compositions in stardust SiC grains from the Murchison meteorite: Insights into the stellar origins of large SiC grains

NASA Astrophysics Data System (ADS)

Ávila, Janaína N.; Ireland, Trevor R.; Gyngard, Frank; Zinner, Ernst; Mallmann, Guilherme; Lugaro, Maria; Holden, Peter; Amari, Sachiko

2013-11-01

We report barium isotopic measurements in 12 large (7-58 μm) stardust silicon carbide grains recovered from the Murchison carbonaceous chondrite. The C-, N-, and Si-isotopic compositions indicate that all 12 grains belong to the mainstream population and, as such, are interpreted to have condensed in the outflows of low-mass carbon-rich asymptotic giant branch (AGB) stars with close-to-solar metallicity. Barium isotopic analyses were carried out on the Sensitive High Resolution Ion Microprobe - Reverse Geometry (SHRIMP-RG) with combined high mass resolution and energy filtering to eliminate isobaric interferences from molecular ions. Contrary to previous measurements in small (<5 μm) mainstream grains, the analyzed large SiC grains do not show the classical s-process enrichment, having near solar Ba isotopic compositions. While contamination with solar material is a common explanation for the lack of large isotopic anomalies in stardust SiC grains, particularly for these large grains which have low trace element abundances, our results are consistent with previous observations that Ba isotopic ratios are dependent on grain size. We have compared the SiC data with theoretical predictions of the evolution of Ba isotopic ratios in the envelopes of low-mass AGB stars with a range of stellar masses and metallicities. The Ba isotopic measurements obtained for large SiC grains from the LS + LU fractions are consistent with grain condensation in the envelope of very low-mass AGB stars (1.25 M⊙) with close-to-solar metallicity, which suggests that conditions for growth of large SiC might be more favorable in very low-mass AGB stars during the early C-rich stages of AGB evolution or in stable structures around AGB stars whose evolution was cut short due to binary interaction, before the AGB envelope had already been largely enriched with the products of s-process nucleosynthesis.

Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

NASA Astrophysics Data System (ADS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.

2015-04-01

Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

S- and Sr-isotopic compositions in barite-silica chimney from the Franklin Seamount, Woodlark Basin, Papua New Guinea: constraints on genesis and temporal variability of hydrothermal fluid

NASA Astrophysics Data System (ADS)

Ray, Durbar; Banerjee, Ranadip; Balakrishnan, S.; Paropkari, Anil L.; Mukhopadhyay, Subir

2017-07-01

Isotopic ratios of strontium and sulfur in six layers across a horizontal section of a hydrothermal barite-silica chimney from Franklin Seamount of western Woodlark Basin have been investigated. Sr-isotopic ratios in barite samples (87Sr/86Sr = 0.70478-0.70493) are less radiogenic than seawater (87Sr/86Sr = 0.70917) indicating that substantial leaching of sub-seafloor magma was involved in the genesis of hydrothermal fluid. The SO2 of magma likely contributed a considerable amount of lighter S-isotope in fluid and responsible for the formation of barite, which is isotopically lighter (δ34S = 19.4-20.5 ‰) than modern seawater (δ34S 21 ‰). The systematic changes in isotopic compositions across the chimney wall suggest temporal changes in the mode of mineral formation during the growth of the chimney. Enrichment of heavy S- and Sr-isotopes (δ34S = 20.58 ‰; 87Sr/86Sr = 0.70493) in the outermost periphery of the chimney indicates that, at the initial stage of chimney development, there was a significant contribution of seawater sulfate during barite mineralization. Thereafter, thickening of chimney wall occurred due to precipitation of fluid carrying more magmatic components relative to seawater. This led to a gradual enrichment of lighter isotopes (δ34S = 20.42-19.48 ‰; 87Sr/86Sr = 0.70491-0.704787) toward the inner portion of the chimney wall. In contrast, the innermost layer surrounding the fluid conduit is characterized by heavier and more radiogenic isotopes (δ34S = 20.3 ‰; 87Sr/86Sr = 0.7049). This suggests there was increasing influence of percolating seawater on the mineral paragenesis at the waning phase of the chimney development.

Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

NASA Astrophysics Data System (ADS)

Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

2017-06-01

Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope fractionation by key enzymes in the sulfate reduction pathway, should provide an empirical basis for a quantitative model relating the magnitude of microbial isotope fractionation to their environmental and physiological controls.

Methane sources and production in the northern Cascadia margin gas hydrate system

USGS Publications Warehouse

Pohlman, J.W.; Kaneko, M.; Heuer, V.B.; Coffin, R.B.; Whiticar, M.

2009-01-01

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The ??13C values of methane range from a minimum value of - 82.2??? on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of - 39.5??? at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from - 22.5??? to +25.7???. The magnitude of the carbon isotope separation between methane and CO2 (??c = 63.8 ?? 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform ??DCH4 values (- 172??? ?? 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5???. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25??? and increases to ~ 40??? at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

A 1.5 Ma record of plume-ridge interaction at the Western Galápagos Spreading Center (91°40‧-92°00‧W)

NASA Astrophysics Data System (ADS)

Herbrich, Antje; Hauff, Folkmar; Hoernle, Kaj; Werner, Reinhard; Garbe-Schönberg, Dieter; White, Scott

2016-07-01

Shallow (elevated) portions of mid-ocean ridges with enriched geochemical compositions near hotspots document the interaction of hot, geochemically-enriched plume mantle with shallow depleted upper mantle. Whereas the spatial variations in geochemical composition of ocean crust along the ridge axis in areas where plume-ridge interaction is taking place have been studied globally, only restricted information exists concerning temporal variations in geochemistry of ocean crust formed through plume-ridge interaction. Here we present a detailed geochemical study of 0-1.5 Ma ocean crust sampled from the Western Galápagos Spreading Center (WGSC) axis to 50 km north of the axis, an area that is presently experiencing a high influx of mantle material from the Galápagos hotspot. The tholeiitic to basaltic andesitic fresh glass and few bulk rock samples have incompatible element abundances and Sr-Nd-Pb isotopic compositions intermediate between depleted normal mid-ocean-ridge basalt (N-MORB) from >95.5°W along the WGSC and enriched lavas from the Galápagos Archipelago, displaying enriched (E-)MORB type compositions. Only limited and no systematic geochemical variations are observed with distance from the ridge axis for <1.0 Ma old WGSC crust, whereas 1.0-1.5 Ma old crust trends to more enriched isotopic compositions in 87Sr/86Sr, 143Nd/144Nd, 207Pb/204Pb and 208Pb/204Pb isotope ratios. On isotope correlation diagrams, the data set displays correlations between depleted MORB and two enriched components. Neither the geographically referenced geochemical domains of the Galápagos Archipelago nor the end members used for principal component analysis can successfully describe the observed mixing relations. Notably an off-axis volcanic cone at site DR63 has the appropriate composition to serve as the enriched component for the younger WGSC and could represent a portion of the northern part of the Galápagos plume not sampled south of the WGSC. Similar compositions to samples from volcanic cone DR63 have been found in the northern part of the 11-14 Ma Galápagos hotspot track offshore Costa Rica, indicating that this composition is derived from the northern portion of the Galápagos plume. The older WGSC requires involvement of an enriched mantle two (EMII) type source, not recognized thus far in the Galápagos system, and is interpreted to reflect entrained material either from small-scale heterogeneities within the upper mantle or from the mantle transition zone. Overall the source material for the 0-1.5 Ma WGSC ocean crust appears to represent mixing of depleted upper mantle with Northern Galápagos Plume material of relatively uniform composition in relatively constant proportions.

Partial Least Squares Calibration Modeling Towards the Multivariate Limit of Detection for Enriched Isotopic Mixtures via Laser Ablation Molecular Isotopic Spectroscopy

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

Harris, Candace; Profeta, Luisa; Akpovo, Codjo

The psuedo univariate limit of detection was calculated to compare to the multivariate interval. ompared with results from the psuedounivariate LOD, the multivariate LOD includes other factors (i.e. signal uncertainties) and the reveals the significance in creating models that not only use the analyte’s emission line but also its entire molecular spectra.

The Chronology and Petrogenesis of the Mare Basalt Clast from Lunar Meteorite Dhofar 287: Rb-Sr and Sm- Nd Isotopic Studies

NASA Technical Reports Server (NTRS)

Shih, C.-Y.; Nyquist, L. E.; Reese, Y.; Wiesmann, H.; Nazarov, M. A.; Taylor, L. A.

2002-01-01

The Sm-Nd isochron for lunar mare basalt meteorite Dhofar 287A yields T = 3.46 +/- 0.03 Ga and Nd = 0.6 +/- 0.3. Its Rb-Sr isotopic system is severely altered. The basalt is unique, probably coming from an enriched mantle source. Additional information is contained in the original extended abstract.

Method of controlling the mercury vapor pressure in a photo-chemical lamp or vapor filter used for Hg.sup.196 enrichment

DOEpatents

Grossman, Mark W.

1993-01-01

The present invention is directed to a method of eliminating the cold spot zones presently used on Hg.sup.196 isotope separation lamps and filters by the use of a mercury amalgams, preferably mercury - indium amalgams. The use of an amalgam affords optimization of the mercury density in the lamp and filter of a mercury enrichment reactor, particularly multilamp enrichment reactors. Moreover, the use of an amalgam in such lamps and/or filters affords the ability to control the spectral line width of radiation emitted from lamps, a requirement for mercury enrichment.

Method of controlling the mercury vapor pressure in a photo-chemical lamp or vapor filter used for Hg[sup 196] enrichment

DOEpatents

Grossman, M.W.

1993-02-16

The present invention is directed to a method of eliminating the cold spot zones presently used on Hg[sup 196] isotope separation lamps and filters by the use of a mercury amalgams, preferably mercury - indium amalgams. The use of an amalgam affords optimization of the mercury density in the lamp and filter of a mercury enrichment reactor, particularly multilamp enrichment reactors. Moreover, the use of an amalgam in such lamps and/or filters affords the ability to control the spectral line width of radiation emitted from lamps, a requirement for mercury enrichment.

Determination of urea kinetics by isotope dilution with [13C]urea and gas chromatography-isotope ratio mass spectrometry (GC-IRMS) analysis.

PubMed

Kloppenburg, W D; Wolthers, B G; Stellaard, F; Elzinga, H; Tepper, T; de Jong, P E; Huisman, R M

1997-07-01

1. Stable urea isotopes can be used to study urea kinetics in humans. The use of stable urea isotopes for studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material. We devised a urea dilution for measurement of the distribution volume, production rate and clearance of urea in healthy subjects and renal failure patients using the inexpensive single labelled [13C]urea isotope with subsequent analysis by headspace chromatography-isotope ratio MS (GC-IRMS) of the [13C]urea enrichment. 2. The method involves measurement of the molar percentage excess of [13C]urea in plasma samples taken over a 4 h period after an intravenous bolus injection of [13C]urea. During the sample processing procedure, the plasma samples together with calibration samples containing a known molar percentage excess of [13C]urea are acidified with phosphoric acid to remove endogenous CO2, and are subsequently incubated with urease to convert the urea present in the plasma samples into CO2. The 13C enrichment of the generated CO2 is analysed by means of GC-IRMS. This method allows measurement of the molar percentage excess of [13C]urea to an accuracy of 0.02%. 3. Reproducibility studies showed that the sample processing procedure [within-run coefficient of variation (CV) < 2.8% and between-run CV < 8.8%] and the GC-IRMS analysis (within-day CV < 1.3% and between-day CV < 1.3%) could be repeated with good reproducibility. 4. In clinical urea kinetic studies in a healthy subject and in a renal failure patient without residual renal function, reproducible values of the distribution volume, production rate and clearance of urea were determined using minimal amounts of [13C]urea (25-50 mg). 5. Because only low [13C]urea enrichments are needed in this urea dilution method using GC-IRMS analysis, the costs of urea kinetic studies are reduced considerably, especially in patients with renal failure.

Zircon Hf-O isotopic constraints on the origin of Late Mesozoic felsic volcanic rocks from the Great Xing'an Range, NE China

NASA Astrophysics Data System (ADS)

Gong, Mingyue; Tian, Wei; Fu, Bin; Wang, Shuangyue; Dong, Jinlong

2018-05-01

The voluminous Late Mesozoic magmatism was related to extensive re-melting of juvenile materials that were added to the Central East Asia continent in Phanerozoic time. The most favoured magma generation mechanism of Late Mesozoic magmas is partial melting of underplated lower crust that had radiogenic Hf-Nd isotopic characteristics, but this mechanism faces difficulties when interpreting other isotopic data. The tectonic environment controlling the generation of the Late Mesozoic felsic magmas is also in dispute. In this study, we obtained new U-Pb ages, and geochemical and isotopic data of representative Jurassic (154.4 ± 1.5 Ma) and Cretaceous (140.2 ± 1.5 Ma) felsic volcanic samples. The Jurassic sample has inherited zircon cores of Permian age, with depleted mantle-like εHf(t) of +7.4 - +8.5, which is in contrast with those of the magmatic zircons (εHf(t) = +2.4 ± 0.7). Whereas the inherited cores and the magmatic zircons have identical mantle-like δ18O composition ranges (4.25-5.29‰ and 4.69-5.54‰, respectively). These Hf-O isotopic characteristics suggest a mixed source of enriched mantle materials rather than ancient crustal components and a depleted mantle source represented by the inherited Permian zircon core. This mechanism is manifested by the eruption of Jurassic alkaline basalts originated from an enriched mantle source. The Cretaceous sample has high εHf(t) of +7.0 - +10.5, suggesting re-melting of a mafic magma derived from a depleted mantle-source. However, the sub-mantle zircon δ18O values (3.70-4.58‰) suggest the depleted mantle-derived mafic source rocks had experienced high temperature hydrothermal alteration at upper crustal level. Therefore, the Cretaceous felsic magma, if not all, could be generated by re-melting of down-dropped supracrustal volcanic rocks that experienced high temperature oxygen isotope alteration. The two processes, enriched mantle-contribution and supracrustal juvenile material re-melting, are new generation mechanisms of the Late Mesozoic magmas from Central East Asia. Rift settings may have controlled these processes throughout crustal and mantle levels.

Stomatal Density Influences Leaf Water and Leaf Wax D/H Values in Arabidopsis

NASA Astrophysics Data System (ADS)

Lee, H.; Feakins, S. J.; Sternberg, L. O.

2014-12-01

The hydrogen isotopic composition (δD) of plant leaf wax is a powerful tool to study the hydrology of past and present environments. The δD value of leaf waxes is known to primarily reflect the δD value of source water, modified by biological fractionations commonly summarized as the 'net or apparent' fractionation. It remains a challenge, however, to quantitatively relate the isotopic composition of the end product (wax) back to that of the precursor (water) because multiple isotope effects contributing to the net fractionation are not yet well understood. Transgenic variants have heretofore unexplored potential to isolate individual isotope effects. Here we report the first hydrogen isotopic measurements from transgenic Arabidopsis thaliana plants with calculations of leaf water enrichment, net and biosynthetic fractionation values from measured δD of plant waters and leaf wax n-alkanes. We employed transgenic Arabidopsis leaves, engineered to have different stomatal density, by differential expression of the stomatal growth hormone stomagen. Comparison of variants and wild types allow us to isolate the effects of stomatal density on leaf water and the net fractionation expressed by leaf wax biomarkers. Results show that transgenic leaves with denser pores have more enriched leaf water and leaf wax δD values than wild type and even more so than transgenic leaves with sparse stomata (difference of 10 ‰). Our findings that stomatal density controls leaf water and leaf wax δD values adds insights into the cause of variations in net fractionations between species, as well as suggesting that geological variations in stomatal density may modulate the sedimentary leaf wax δD record. In nature, stomatal density varies between species and environments, and all other factors being equal, this will contribute to variations in fractionations observed. Over geological history, lower stomatal densities occur at times of elevated pCO2; our findings predict reduced leaf water isotopic enrichment and larger net fractionations during these greenhouse conditions. Future work involving transgenic plants holds considerable potential to isolate additional factors which may influence the net fractionation between source water and leaf waxes adding to our fundamental understanding of this proxy.

Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

NASA Technical Reports Server (NTRS)

Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

2013-01-01

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Application of Nitrogen and Carbon Stable Isotopes (δ15N and δ13C) to Quantify Food Chain Length and Trophic Structure

PubMed Central

Perkins, Matthew J.; McDonald, Robbie A.; van Veen, F. J. Frank; Kelly, Simon D.; Rees, Gareth; Bearhop, Stuart

2014-01-01

Increasingly, stable isotope ratios of nitrogen (δ15N) and carbon (δ13C) are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR) using δ15N, and carbon range (CR) using δ13C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ15N or δ13C from source to consumer) between trophic levels and among food chains. δ15N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰), and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ13C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ13C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority of ecological systems. PMID:24676331