Sample records for isotope abundance analysis

  1. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-02

    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  2. Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

    DOEpatents

    Harney, Robert C.; Bloom, Stewart D.

    1978-01-01

    Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances.

  3. Ar39 Detection at the 10-16 Isotopic Abundance Level with Atom Trap Trace Analysis

    NASA Astrophysics Data System (ADS)

    Jiang, W.; Williams, W.; Bailey, K.; Davis, A. M.; Hu, S.-M.; Lu, Z.-T.; O'Connor, T. P.; Purtschert, R.; Sturchio, N. C.; Sun, Y. R.; Mueller, P.

    2011-03-01

    Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric Ar39 (half-life=269yr), a cosmogenic isotope with an isotopic abundance of 8×10-16. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

  4. Reporting of nitrogen-isotope abundances (Technical Report)

    USGS Publications Warehouse

    Coplen, Tyler B.; Krouse, H.R.; Böhlke, John Karl

    1992-01-01

    To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14N/15N value of N2 in air for calculating atom percent 15N from measured δ15N values.

  5. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

    During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

  6. Isotope-abundance variations of selected elements (IUPAC technical report)

    USGS Publications Warehouse

    Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

    2002-01-01

    Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

  7. Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

    PubMed

    Tea, Illa; Tcherkez, Guillaume

    2017-01-01

    The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

  8. Calcium isotope analysis by mass spectrometry.

    PubMed

    Boulyga, Sergei F

    2010-01-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use

  9. An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1977-01-01

    An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

  10. Calcium Isotope Analysis by Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Boulyga, S.; Richter, S.

    2010-12-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

  11. Elemental and isotopic abundances in the solar wind

    NASA Technical Reports Server (NTRS)

    Geiss, J.

    1972-01-01

    The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

  12. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

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

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.

    2009-12-01

    This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate componentsmore » can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development

  13. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

    During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

  14. Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

    NASA Technical Reports Server (NTRS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Rossman, George R.; Eiler, John M.; Neal, Clive R.

    2015-01-01

    The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands.

  15. Isotopic abundance in atom trap trace analysis

    DOEpatents

    Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

    2014-03-18

    A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

  16. Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

    NASA Technical Reports Server (NTRS)

    Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

    2009-01-01

    Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

  17. Specific activity and isotope abundances of strontium in purified strontium-82

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

    Fitzsimmons, J. M.; Medvedev, D. G.; Mausner, L. F.

    2015-11-12

    A linear accelerator was used to irradiate a rubidium chloride target with protons to produce strontium-82 (Sr-82), and the Sr-82 was purified by ion exchange chromatography. The amount of strontium associated with the purified Sr-82 was determined by either: ICP-OES or method B which consisted of a summation of strontium quantified by gamma spectroscopy and ICP-MS. The summation method agreed within 10% to the ICP-OES for the total mass of strontium and the subsequent specific activities were determined to be 0.25–0.52 TBq mg -1. Method B was used to determine the isotope abundances by weight% of the purified Sr-82, andmore » the abundances were: Sr-82 (10–20.7%), Sr-83 (0–0.05%), Sr-84 (35–48.5%), Sr-85 (16–25%), Sr-86 (12.5–23%), Sr-87 (0%), and Sr-88 (0–10%). The purified strontium contained mass amounts of Sr-82, Sr-84, Sr-85, Sr-86, and Sr-88 in abundances not associated with natural abundance, and 90% of the strontium was produced by the proton irradiation. A comparison of ICP-OES and method B for the analysis of Sr-82 indicated analysis by ICP-OES would be easier to determine total mass of strontium and comply with regulatory requirements. An ICP-OES analytical method for Sr-82 analysis was established and validated according to regulatory guidelines.« less

  18. Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Klaue, B.; Blum, J. D.; Buseck, P. R.

    2001-01-01

    The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation

  19. Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

    USGS Publications Warehouse

    Coplen, Tyler B.; Shrestha, Yesha

    2016-01-01

    There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

  20. Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

    USGS Publications Warehouse

    Meier, A.L.

    1982-01-01

    The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

  1. Natural abundances of carbon isotopes in acetate from a coastal marine sediment

    NASA Technical Reports Server (NTRS)

    Blair, N. E.; Martens, C. S.; Des Marais, D. J.

    1987-01-01

    Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

  2. System and method for high precision isotope ratio destructive analysis

    DOEpatents

    Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

    2013-07-02

    A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

  3. Carbon-13 Isotopic Abundance and Concentration of Atmospheric Methane for Background Air in the Southern and Northern Hemispheres from 1978 to 1989 (NDP-049)

    DOE Data Explorer

    Stevens, C. M. [Chemical Technology Division, Argonne National Laboratory, Argonne, Illinois (USA)

    2012-01-01

    This data package presents atmospheric CH4 concentration and 13C isotopic abundance data derived from air samples collected over the period 1978-1989 at globally distributed clean-air sites. The data set comprises 201 records, 166 from the Northern Hemisphere and 35 from the Southern Hemisphere. The air samples were collected mostly in rural or marine locations remote from large sources of CH4 and are considered representative of tropospheric background conditions. The air samples were processed by isolation of CH4 from air and conversion to CO2 for isotopic analysis by isotope ratio mass spectrometry. These data represent one of the earliest records of 13C isotopic yy!measurements for atmospheric methane and have been used to refine estimates of CH4 emissions, calculate annual growth rates of emissions from changing sources, and provide evidence for changes in the rate of atmospheric removal of CH4. The data records consist of sample collection date; number of samples combined for analysis; sampling location; analysis date; CH4 concentration; 13C isotopic abundance; and flag codes to indicate outliers, repeated analyses, and other information.

  4. Laser spectrometer for CO2 clumped isotope analysis

    NASA Astrophysics Data System (ADS)

    Prokhorov, Ivan; Kluge, Tobias; Janssen, Christof

    2017-04-01

    Carbon dioxide clumped isotope thermometry has proven to be a reliable method for biogeochemical and atmospheric research. We present a new laser spectroscopic instrument for doubly-substituted isotopologues analysis. In contrast to a conventional isotope ratio mass spectrometry (IRMS), tunable laser direct absorption spectroscopy (TLDAS) has the advantage of isotopologue-specific determination free of isobaric interferences. Tunable infrared laser based spectrometer for clumped isotope analysis is being developed in collaboration between Heidelberg University, Germany, and LERMA-IPSL, CNRS, France. The instrument employs two continuous intraband cascade lasers (ICL) tuned at 4439 and 4329 nm. The spectral windows covered by the lasers contain absorption lines of the six most abundant CO2 isotopologues, including the two doubly substituted species 16O13C18O and 16O13C17O, and all singly substituted isotopologues with 13C, 18O and 17O. A Herriott-type multi-pass cell provides two different absorption pathlengths to compensate the abundance difference between singly- and doubly-substituted isotopologues. We have reached the sub-permill precision required for clumped isotope measurements within the integration time of several seconds. The test version of the instrument demonstrates a performance comparable to state of the art IRMS. We highlight the following features of the instrument that are strong advantages compared to conventional mass spectrometry: measurement cycle in the minute range, simplified sample preparation routine, table-top layout with a potential for in-situ applications.

  5. Further analysis of the IRIS iron isotope experiment

    NASA Technical Reports Server (NTRS)

    Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

    1980-01-01

    The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  7. Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

    NASA Technical Reports Server (NTRS)

    Rau, G. H.; Desmarais, David J.

    1985-01-01

    Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

  8. Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur

    NASA Astrophysics Data System (ADS)

    Ding, T.; Valkiers, S.; Kipphardt, H.; De Bièvre, P.; Taylor, P. D. P.; Gonfiantini, R.; Krouse, R.

    2001-08-01

    Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag2S materials enriched in32S, 33S, and 34S. All materials were converted into SF6 gas and subsequently, their sulfur isotope ratios were measured on the SF5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

  9. Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

    2016-09-01

    Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

  10. 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

  11. Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

    PubMed Central

    Kaur, Parminder; O’Connor, Peter B.

    2008-01-01

    Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

  12. Isotopic Abundances as Tracers of the Processes of Lunar Formation

    NASA Astrophysics Data System (ADS)

    Pahlevan, K.

    2011-12-01

    Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly

  13. Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

    NASA Technical Reports Server (NTRS)

    Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

    1994-01-01

    The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

  14. Advances in natural stable isotope ratio analysis of human hair to determine nutritional and metabolic status.

    PubMed

    Petzke, Klaus J; Fuller, Benjamin T; Metges, Cornelia C

    2010-09-01

    We review the literature on the use of stable isotope ratios at natural abundance to reveal information about dietary habits and specific nutrient intakes in human hair protein (keratin) and amino acids. In particular, we examine whether hair isotopic compositions can be used as unbiased biomarkers to provide information about nutritional status, metabolism, and diseases. Although the majority of research on the stable isotope ratio analysis of hair has focused on bulk protein, methods have been recently employed to examine amino acid-specific isotope ratios using gas chromatography or liquid chromatography coupled to an isotope ratio mass spectrometer. The isotopic measurement of amino acids has the potential to answer research questions on amino acid nutrition, metabolism, and disease processes and can contribute to a better understanding of the variations in bulk protein isotope ratio values. First results suggest that stable isotope ratios are promising as unbiased nutritional biomarkers in epidemiological research. However, variations in stable isotope ratios of human hair are also influenced by nutrition-dependent nitrogen balance, and more controlled clinical research is needed to examine these effects in human hair. Stable isotope ratio analysis at natural abundance in human hair protein offers a noninvasive method to reveal information about long-term nutritional exposure to specific nutrients, nutritional habits, and in the diagnostics of diseases leading to nutritional stress and impaired nitrogen balance.

  15. The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

    NASA Astrophysics Data System (ADS)

    Stüeken, E. E.; Buick, R.; Bekker, A.; Catling, D.; Foriel, J.; Guy, B. M.; Kah, L. C.; Machel, H. G.; Montañez, I. P.; Poulton, S. W.

    2015-08-01

    The Earth's surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2 Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth's history and all are mass-dependent within error. In the Archean, especially after 2.7 Gyr, we find an isotopic enrichment in marine (+0.37 ± 0.27‰) relative to non-marine samples (-0.28 ± 0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42 ± 0.45‰ to a Phanerozoic mean of -0.19 ± 0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of

  16. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    NASA Astrophysics Data System (ADS)

    Tea, Illa; Martineau, Estelle; Antheaume, Ingrid; Lalande, Julie; Mauve, Caroline; Gilard, Francoise; Barillé-Nion, Sophie; Blackburn, Anneke C.; Tcherkez, Guillaume

    2016-09-01

    Breast cancer is the most common cancer in women worldwide. Despite the information provided by anatomopathological assessment and molecular markers (such as receptor expression ER, PR, HER2), breast cancer therapies and prognostics depend on the metabolic properties of tumor cells. However, metabolomics have not provided a robust and congruent biomarker yet, likely because individual metabolite contents are insufficient to encapsulate all of the alterations in metabolic fluxes. Here, we took advantage of natural 13C and 15N isotope abundance to show there are isotopic differences between healthy and cancer biopsy tissues or between healthy and malignant cultured cell lines. Isotope mass balance further suggests that these differences are mostly related to lipid metabolism, anaplerosis and urea cycle, three pathways known to be impacted in malignant cells. Our results demonstrate that the isotope signature is a good descriptor of metabolism since it integrates modifications in C partitioning and N excretion altogether. Our present study is thus a starting point to possible clinical applications such as patient screening and biopsy characterization in every cancer that is associated with metabolic changes.

  17. Potassium isotope abundances in Australasian tektites and microtektites.

    NASA Astrophysics Data System (ADS)

    Herzog, G. F.; O'D. Alexander, C. M.; Berger, E. L.; Delaney, J. S.; Glass, B. P.

    2008-10-01

    We report electron microprobe determinations of the elemental compositions of 11 Australasian layered tektites and 28 Australasian microtektites; and ion microprobe determinations of the 41K/39K ratios of all 11 tektites and 13 of the microtektites. The elemental compositions agree well with literature values, although the average potassium concentrations measured here for microtektites, 1.1 1.6 wt%, are lower than published average values, 1.9 2.9 wt%. The potassium isotope abundances of the Australasian layered tektites vary little. The average value of δ41K, 0.02 ± 0.12‰ (1σ mean), is indistinguishable from the terrestrial value (= 0 by definition) as represented by our standard, thereby confirming four earlier tektite analyses of Humayun and Koeberl (2004). In agreement with those authors, we conclude that evaporation has significantly altered neither the isotopic nor the elemental composition of Australasian layered tektites for elements less volatile than potassium. Although the average 41K/39K ratio of the microtektites, 1.1 ± 1.7‰ (1σ mean), is also statistically indistinguishable from the value for the standard, the individual ratios vary over a very large range, from -10.6 ± 1.4‰ to +13.8 ± 1.5‰ and at least three of them are significantly different from zero. We interpret these larger variations in terms of the evaporation of isotopically light potassium; condensation of potassium in the vapor plume; partial or complete stirring and quenching of the melts; and the possible uptake of potassium from seawater. That the average 41K/39K ratio of the microtektites equals the terrestrial value suggests that the microtektite-forming system was compositionally closed with respect to potassium and less volatile elements. The possibility remains open that 41K/39K ratios of microtektites vary systematically with location in the strewn field.

  18. Study on strontium isotope abundance-ratio measurements by using a 13-MeV proton beam

    NASA Astrophysics Data System (ADS)

    Jeong, Cheol-Ki; Jang, Han; Lee, Goung-Jin

    2016-09-01

    The Rb-Sr dating method is used in dating Paleozoic and Precambrian rocks. This method measures the 87Rb and the 87Sr concentrations by using thermal ionization mass spectrometry (TIMS) [J. Hefne et al., Inter. J. Phys. Sci. 3(1), 28 (2008)]. In addition, it calculates the initial 87Sr/86Sr ratio to increase the reliability of Rb-Sr dating. In this study, the 87Sr/86Sr ratio was measured by using a 13-MeV proton accelerator. Proton kinetic energies are in the range of tens of megaelectronvolts, and protons have large absorption cross-sections for ( p, n) reactions with most substances. After absorbing a proton with such a high kinetic energy, an element is converted into a nuclide with its atomic number increased by one via nuclear transmutation. These nuclides usually have short half-lives and return to the original state through radioactive decay. When a strontium sample is irradiated with protons, nuclear transmutation occurs; thus, the strontium isotope present in the sample changes to a yttrium isotope, which is an activated radioisotope. Based on this, the 87Sr/86Sr ratio was calculated by analyzing the gamma-rays emitted by each yttrium isotope. The KIRAMS-13 cyclotron at the Cyclotron Center of Chosun University, where 13-MeV protons can be extracted, was utilized in our experiment. The 87Sr/86Sr isotope ratio was computed for samples irradiated with these protons, and the result was similar to the isotope ratio for the Standard Reference Material, i.e., 98.2 ± 3.4%. As part of the analysis, proton activation analyses were performed using 13-MeV protons, and the experimental results of this research suggest a possible approach for measuring the strontium-isotope abundance ratio of samples.

  19. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  20. Relative and accurate measurement of protein abundance using 15N stable isotope labeling in Arabidopsis (SILIA).

    PubMed

    Guo, Guangyu; Li, Ning

    2011-07-01

    In the quantitative proteomic studies, numerous in vitro and in vivo peptide labeling strategies have been successfully applied to measure differentially regulated protein and peptide abundance. These approaches have been proven to be versatile and repeatable in biological discoveries. (15)N metabolic labeling is one of these widely adopted and economical methods. However, due to the differential incorporation rates of (15)N or (14)N, the labeling results produce imperfectly matched isotopic envelopes between the heavy and light nitrogen-labeled peptides. In the present study, we have modified the solid Arabidopsis growth medium to standardize the (15)N supply, which led to a uniform incorporation of (15)N into the whole plant protein complement. The incorporation rate (97.43±0.11%) of (15)N into (15)N-coded peptides was determined by correlating the intensities of peptide ions with the labeling efficiencies according to Gaussian distribution. The resulting actual incorporation rate (97.44%) and natural abundance of (15)N/(14)N-coded peptides are used to re-calculate the intensities of isotopic envelopes of differentially labeled peptides, respectively. A modified (15)N/(14)N stable isotope labeling strategy, SILIA, is assessed and the results demonstrate that this approach is able to differentiate the fold change in protein abundance down to 10%. The machine dynamic range limitation and purification step will make the precursor ion ratio deriving from the actual ratio fold change. It is suggested that the differentially mixed (15)N-coded and (14)N-coded plant protein samples that are used to establish the protein abundance standard curve should be prepared following a similar protein isolation protocol used to isolate the proteins to be quantitated. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

  1. Isotopic abundances of Hg in mercury stars inferred from the Hg II line at 3984 A

    NASA Technical Reports Server (NTRS)

    White, R. E.; Vaughan, A. H., Jr.; Preston, G. W.; Swings, J. P.

    1976-01-01

    Wavelengths of the Hg II absorption feature at 3984 A in 30 Hg stars are distributed uniformly from the value for the terrestrial mix to a value that corresponds to nearly pure Hg-204. The wavelengths are correlated loosely with effective temperatures inferred from Q(UBV). Relative isotopic abundances derived from partially resolved profiles of the 3984-A line in iota CrB, chi Lup, and HR 4072 suggest that mass-dependent fractionation has occurred in all three stars. It is supposed that such fractionation occurs in all Hg stars, and a scheme whereby isotopic compositions can be inferred from a comparison of stellar wavelengths and equivalent widths with those calculated for a family of fractionated isotopic mixes. Theoretical profiles calculated for the derived isotopic composition agree well with high-resolution interferometric profiles obtained for three of the stars.

  2. Meteoritic Sulfur Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Thiemens, Mark H.

    1996-01-01

    Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

  3. Using stable isotope analysis to discriminate gasoline on the basis of its origin.

    PubMed

    Heo, Su-Young; Shin, Woo-Jin; Lee, Sin-Woo; Bong, Yeon-Sik; Lee, Kwang-Sik

    2012-03-15

    Leakage of gasoline and diesel from underground tanks has led to a severe environmental problem in many countries. Tracing the production origin of gasoline and diesel is required to enable the development of dispute resolution and appropriate remediation strategies for the oil-contaminated sites. We investigated the bulk and compound-specific isotopic compositions of gasoline produced by four oil companies in South Korea: S-Oil, SK, GS and Hyundai. The relative abundance of several compounds in gasoline was determined by the peak height of the major ion (m/z 44). The δ(13)C(Bulk) and δD(Bulk) values of gasoline produced by S-Oil were significantly different from those of SK, GS and Hyundai. In particular, the compound-specific isotopic value (δ(13)C(CSIA)) of methyl tert-butyl ether (MTBE) in S-Oil gasoline was significantly lower than that of gasoline produced by other oil companies. The abundance of several compounds in gasoline, such as n-pentane, MTBE, n-hexane, toluene, ethylbenzene and o-xylene, differed widely among gasoline from different oil companies. This study shows that gasoline can be forensically discriminated according to the oil company responsible for its manufacture using stable isotope analysis combined with multivariate statistical analysis. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

    NASA Technical Reports Server (NTRS)

    Blake, Geoffrey A.

    2004-01-01

    We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These

  5. Isotopic analysis of individual refractory metal nuggets using atom probe tomography

    NASA Astrophysics Data System (ADS)

    Daly, L.; Bland, P.; Schaefer, B. F.; Saxey, D. W.; Reddy, S.; Fougerouse, D.; William, R. D. A.; Forman, L. V.; Trimby, P.; La Fontaine, A.; Yang, L.; Cairney, J.; Ringer, S.

    2016-12-01

    Sub-micrometre metallic alloys of the highly siderophile elements, known as refractory metal nuggets (RMNs), can be found in primitive carbonaceous chondrites. There has been some suggestion that these grains may have a pre-solar origin, however their <1 µm size has meant that isotopic analysis of individual grains has not previously been possible. Atom probe microscopy has sufficient spatial resolution to quantify the isotopic compositions, across the entire mass range, of small sample volumes (<0.02 µm3) with high sensitivity and precision. We present analyses of four individual RMNs from the same refractory inclusion within the ALH 77307 meteorite. The results indicate that these RMNs have significant isotopic deviations from solar relative isotope abundances and therefore preserve a pre-solar isotopic signature. All RMNs exhibit large p-process enrichments in 98Ru and depletions in s-process 186Os. Two RMNs have a similar isotopic signature, suggesting formation in the same stellar environment. This similarity between two RMNs indicates that there may be a significant contribution of material to our solar system from a single source. The other two RMNs are isotopically dissimilar. Finally, three of the RMNs plot on a 187Re -187Os isochron from which we can derive a galactic age of 12.5 Ga ±1.8. To the best of our knowledge this is the first direct determination of the age of the Milky Way through physical analysis of non-solar material.

  6. Stable isotope analysis of Dacryoconarid carbonate microfossils: a new tool for Devonian oxygen and carbon isotope stratigraphy.

    PubMed

    Frappier, Amy Benoit; Lindemann, Richard H; Frappier, Brian R

    2015-04-30

    Dacryoconarids are extinct marine zooplankton known from abundant, globally distributed calcite microfossils in the Devonian, but their shell stable isotope composition has not been previously explored. Devonian stable isotope stratigraphy is currently limited to less common invertebrates or bulk rock analyses of uncertain provenance. As with Cenozoic planktonic foraminifera, isotopic analysis of dacryoconarid shells could facilitate higher-resolution, geographically widespread stable isotope records of paleoenvironmental change, including marine hypoxia events, climate changes, and biocrises. We explored the use of Dacryoconarid isotope stratigraphy as a viable method in interpreting paleoenvironments. We applied an established method for determining stable isotope ratios (δ(13) C, δ(18) O values) of small carbonate microfossils to very well-preserved dacryoconarid shells. We analyzed individual calcite shells representing five common genera using a Kiel carbonate device coupled to a MAT 253 isotope ratio mass spectrometer. Calcite shell δ(13) C and δ(18) O values were compared by taxonomic group, rock unit, and locality. Single dacryoconarid calcite shells are suitable for stable isotope analysis using a Kiel-IRMS setup. The dacryoconarid shell δ(13) C values (-4.7 to 2.3‰) and δ(18) O values (-10.3 to -4.8‰) were consistent across taxa, independent of shell size or part, but varied systematically through time. Lower fossil δ(18) O values were associated with warmer water temperature and more variable δ(13) C values were associated with major bioevents. Dacryoconarid δ(13) C and δ(18) O values differed from bulk rock carbonate values. Dacryoconarid individual microfossil δ(13) C and δ(18) O values are highly sensitive to paleoenvironmental changes, thus providing a promising avenue for stable isotope chemostratigraphy to better resolve regional to global paleoceanographic changes throughout the upper Silurian to the upper Devonian. Our results

  7. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  8. Characteristics of Martian Crustal Materials and Implications for Magmatic Assimilation: Preliminary Re-Os Isotope and Highly Siderophile Element Abundance Data for Nakhlites and Tissint

    NASA Astrophysics Data System (ADS)

    Mari, N.; Riches, A. J. V.; Hallis, L. J.; Lee, M. R.

    2017-07-01

    This project, for the first time, aims to integrate nakhlite Os-isotope compositions and HSE abundance data with S-isotope compositions for sample fractions for which textural information is constrained prior to destructive analyses.

  9. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  10. Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Sahai, R.

    1987-01-01

    Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

  11. The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

    ERIC Educational Resources Information Center

    O'Malley, Rebecca M.

    1982-01-01

    Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

  12. Rhenium-osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites

    NASA Astrophysics Data System (ADS)

    Riches, Amy J. V.; Day, James M. D.; Walker, Richard J.; Simonetti, Antonio; Liu, Yang; Neal, Clive R.; Taylor, Lawrence A.

    2012-11-01

    Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201-0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10-15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056-0.1195), as well as low-Re/Os (0.03-0.13), Pd/Os (0.071-0.946), and relatively low-Pt/Os (0.792-2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage. The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are

  13. A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

    USGS Publications Warehouse

    Sigman, D.M.; Casciotti, K.L.; Andreani, M.; Barford, C.; Galanter, M.; Böhlke, J.K.

    2001-01-01

    We report a new method for measurement of the isotopic composition of nitrate (NO3-) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N2O) generated from nitrate by denitrifying bacteria that lack N2O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

  14. Isotopic Compositions of the Elements, 2001

    NASA Astrophysics Data System (ADS)

    Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

    2005-03-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

  15. Natural-abundance stable carbon isotopes of small-subunit ribosomal RNA (SSU rRNA) from Guaymas Basin (Mexico)

    NASA Astrophysics Data System (ADS)

    MacGregor, B. J.; Mendlovitz, H.; Albert, D.; Teske, A. P.

    2012-12-01

    Small-subunit ribosomal RNA (SSU rRNA) is a phylogenetically informative molecule found in all species. Because it is poorly preserved in most environments, it is a useful marker for active microbial populations. We are using the natural-abundance stable carbon isotopic composition of specific microbial groups to help identify the carbon substrates contributing to microbial biomass in a variety of marine environments. At Guaymas Basin, hydrothermal fluids interact with abundant sedimentary organic carbon to produce natural gas and petroleum. Where this reaches the sediment surface, it can support dense patches of seafloor life, including Beggiatoa mats. We report here on the stable carbon isotopic composition of SSU rRNA from a Beggiatoa mat transect, a cold background site, a warm site with high oil concentration, and a second Beggiatoa mat. The central part of the transect mat overlay the steepest temperature gradient, and was visually dominated by orange Beggiatoa. This was fringed by white Beggiatoa mat and bare, but still warm, sediment. Methane concentrations were saturating beneath the orange and white mats and at the oily site, lower beneath bare sediment, and below detection at the background site. Our initial hypotheses were that rRNA isotopic composition would be strongly influenced by methane supply, and that archaeal rRNA might be lighter than bacterial due to contributions from methanogens and anaerobic methane oxidizers. We used biotin-labeled oligonucleotides to capture Bacterial and Archaeal SSU rRNA for isotopic determination. Background-site rRNA was isotopically heaviest, and bacterial RNA from below 2 cm at the oily site was lightest, consistent with control by methane. Within the transect mat, however, the pattern was more complicated; at some sediment depths, rRNA from the mat periphery was isotopically lightest. Part of this may be due to the spatially and temporally variable paths followed by hydrothermal fluid, which can include horizontal

  16. Accurate experimental determination of the isotope effects on the triple point temperature of water. II. Combined dependence on the 18O and 17O abundances

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    This paper is the second of two articles on the quantification of isotope effects on the triple point temperature of water. In this second article, we address the combined effects of 18O and 17O isotopes. We manufactured five triple point cells with waters with 18O and 17O abundances exceeding widely the natural abundance range while maintaining their natural 18O/17O relationship. The 2H isotopic abundance was kept close to that of VSMOW (Vienna Standard Mean Ocean Water). These cells realized triple point temperatures ranging between  -220 μK to 1420 μK with respect to the temperature realized by a triple point cell filled with VSMOW. Our experiment allowed us to determine an accurate and reliable value for the newly defined combined 18, 17O correction parameter of AO  =  630 μK with a combined uncertainty of 10 μK. To apply this correction, only the 18O abundance of the TPW needs to be known (and the water needs to be of natural origin). Using the results of our two articles, we recommend a correction equation along with the coefficient values for isotopic compositions differing from that of VSMOW and compare the effect of this new equation on a number of triple point cells from the literature and from our own institute. Using our correction equation, the uncertainty in the isotope correction for triple point cell waters used around the world will be  <1 μK.

  17. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-01-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

  18. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-09-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

  19. Precision and long-term stability of clumped-isotope analysis of CO2 using a small-sector isotope ratio mass spectrometer.

    PubMed

    Yoshida, Naohiro; Vasilev, Mikhail; Ghosh, Prosenjit; Abe, Osamu; Yamada, Keita; Morimoto, Maki

    2013-01-15

    The ratio of the measured abundance of (13)C-(18)O bonding CO(2) to its stochastic abundance, prescribed by the δ(13)C and δ(18)O values from a carbonate mineral, is sensitive to its growth temperature. Recently, clumped-isotope thermometry, which uses this ratio, has been adopted as a new tool to elucidate paleotemperatures quantitatively. Clumped isotopes in CO(2) were measured with a small-sector isotope ratio mass spectrometer. CO(2) samples digested from several kinds of calcium carbonates by phosphoric acid at 25 °C were purified using both cryogenic and gas-chromatographic separations, and their isotopic composition (δ(13)C, δ(18)O, Δ(47), Δ(48) and Δ(49) values) were then determined using a dual-inlet Delta XP mass spectrometer. The internal precisions of the single gas Δ(47) measurements were 0.005 and 0.02‰ (1 SE) for the optimum and the routine analytical conditions, respectively, which are comparable with those obtained using a MAT 253 mass spectrometer. The long-term variations in the Δ(47) values for the in-house working standard and the heated CO(2) gases since 2007 were close to the routine, single gas uncertainty while showing seasonal-like periodicities with a decreasing trend. Unlike the MAT 253, the Delta XP did not show any significant relationship between the Δ(47) and δ(47) values. The Delta XP gave results that were approximately as precise as those of the MAT 253 for clumped-isotope analysis. The temporal stability of the Delta XP seemed to be lower, although an advantage of the Delta XP was that no dependency of δ(47) on Δ(47) was found. Copyright © 2012 John Wiley & Sons, Ltd.

  20. A history of violence: Insights into post-accretionary heating in carbonaceous chondrites from volatile element abundances, Zn isotopes and water contents

    NASA Astrophysics Data System (ADS)

    Mahan, Brandon; Moynier, Frédéric; Beck, Pierre; Pringle, Emily A.; Siebert, Julien

    2018-01-01

    Carbonaceous chondrites (CCs) may have been the carriers of water, volatile and moderately volatile elements to Earth. Investigating the abundances of these elements, their relative volatility, and isotopes of state-change tracer elements such as Zn, and linking these observations to water contents, provide vital information on the processes that govern the abundances and isotopic signatures of these species in CCs and other planetary bodies. Here we report Zn isotopic data for 28 CCs (20 CM, 6 CR, 1 C2-ung, and 1 CV3), as well as trace element data for Zn, In, Sn, Tl, Pb, and Bi in 16 samples (8 CM, 6 CR, 1 C2-ung, and 1 CV3), that display a range of elemental abundances from case-normative to intensely depleted. We use these data, water content data from literature and Zn isotopes to investigate volatile depletions and to discern between closed and open system heating. Trace element data have been used to construct relative volatility scales among the elements for the CM and CR chondrites. From least volatile to most, the scale in CM chondrites is Pb-Sn-Bi-In-Zn-Tl, and for CR chondrites it is Tl-Zn-Sn-Pb-Bi-In. These observations suggest that heated CM and CR chondrites underwent volatile loss under different conditions to one another and to that of the solar nebula, e.g. differing oxygen fugacities. Furthermore, the most water and volatile depleted samples are highly enriched in the heavy isotopes of Zn. Taken together, these lines of evidence strongly indicate that heated CM and CR chondrites incurred open system heating, stripping them of water and volatiles concomitantly, during post-accretionary shock impact(s).

  1. ATTA - A New Method of Ultrasensitive Trace-Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Lu, Z.-T.; Bailey, K.; Chen, C. Y.; Du, X.; Li, Y. M.; O'Connor, T. P.; Young, L.; Winkler, G.

    2000-10-01

    We have developed a new method of ultrasensitive trace-isotope analysis based upon the technique of laser manipulation of neutral atoms [1]. This new method allows us to count individual 85Kr and 81Kr atoms present in a natural krypton sample with isotopic abundances in the range of 10-11 and 10-13, respectively. Isotope analysis of 81Kr can be used to date polar ice, and 85Kr is a tracer used in monitoring nuclear wastes. In this experiment metastable Kr atoms were produced in a discharge, decelerated via the Zeeman slowing technique, and captured by a Magneto-Optical Trap where the atoms were counted by measuring their fluorescence. At present our system is capable of counting, in average, one 81Kr atom for about 12 minutes with a total efficiency of 2x10-7. We are currently working to improve our system efficiency by applying cryogenic cooling to the Kr atoms in the discharge region and by recirculating the gas in the vacuum system. This method can be used to analyze many other isotope tracers for a wide range of applications including measuring solar neutrino flux, searching for exotic particles, tracing atmospheric and oceanic currents, archeological and geological dating, medical diagnostics, monitoring fission products in the environment for nuclear waste management, etc. This work is supported by the U.S. Department of Energy, Nuclear Physics Division; L.Young is supported by the Office of Basic Energy Sciences, Division of Chemical Sciences (Contract W-31-109-ENG-38). [1] C.Y. Chen et. al., Science 286, 1139 (1999).

  2. Isotopic compositions of the elements, 2001

    USGS Publications Warehouse

    Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

    2005-01-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

  3. UNiquant, a program for quantitative proteomics analysis using stable isotope labeling.

    PubMed

    Huang, Xin; Tolmachev, Aleksey V; Shen, Yulei; Liu, Miao; Huang, Lin; Zhang, Zhixin; Anderson, Gordon A; Smith, Richard D; Chan, Wing C; Hinrichs, Steven H; Fu, Kai; Ding, Shi-Jian

    2011-03-04

    Stable isotope labeling (SIL) methods coupled with nanoscale liquid chromatography and high resolution tandem mass spectrometry are increasingly useful for elucidation of the proteome-wide differences between multiple biological samples. Development of more effective programs for the sensitive identification of peptide pairs and accurate measurement of the relative peptide/protein abundance are essential for quantitative proteomic analysis. We developed and evaluated the performance of a new program, termed UNiquant, for analyzing quantitative proteomics data using stable isotope labeling. UNiquant was compared with two other programs, MaxQuant and Mascot Distiller, using SILAC-labeled complex proteome mixtures having either known or unknown heavy/light ratios. For the SILAC-labeled Jeko-1 cell proteome digests with known heavy/light ratios (H/L = 1:1, 1:5, and 1:10), UNiquant quantified a similar number of peptide pairs as MaxQuant for the H/L = 1:1 and 1:5 mixtures. In addition, UNiquant quantified significantly more peptides than MaxQuant and Mascot Distiller in the H/L = 1:10 mixtures. UNiquant accurately measured relative peptide/protein abundance without the need for postmeasurement normalization of peptide ratios, which is required by the other programs.

  4. UNiquant, a Program for Quantitative Proteomics Analysis Using Stable Isotope Labeling

    PubMed Central

    Huang, Xin; Tolmachev, Aleksey V.; Shen, Yulei; Liu, Miao; Huang, Lin; Zhang, Zhixin; Anderson, Gordon A.; Smith, Richard D.; Chan, Wing C.; Hinrichs, Steven H.; Fu, Kai; Ding, Shi-Jian

    2011-01-01

    Stable isotope labeling (SIL) methods coupled with nanoscale liquid chromatography and high resolution tandem mass spectrometry are increasingly useful for elucidation of the proteome-wide differences between multiple biological samples. Development of more effective programs for the sensitive identification of peptide pairs and accurate measurement of the relative peptide/protein abundance are essential for quantitative proteomic analysis. We developed and evaluated the performance of a new program, termed UNiquant, for analyzing quantitative proteomics data using stable isotope labeling. UNiquant was compared with two other programs, MaxQuant and Mascot Distiller, using SILAC-labeled complex proteome mixtures having either known or unknown heavy/light ratios. For the SILAC-labeled Jeko-1 cell proteome digests with known heavy/light ratios (H/L = 1:1, 1:5, and 1:10), UNiquant quantified a similar number of peptide pairs as MaxQuant for the H/L = 1:1 and 1:5 mixtures. In addition, UNiquant quantified significantly more peptides than MaxQuant and Mascot Distiller in the H/L = 1:10 mixtures. UNiquant accurately measured relative peptide/protein abundance without the need for post-measurement normalization of peptide ratios, which is required by the other programs. PMID:21158445

  5. ISO/GUM UNCERTAINTIES AND CIAAW (UNCERTAINTY TREATMENT FOR RECOMMENDED ATOMIC WEIGHTS AND ISOTOPIC ABUNDANCES)

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

    HOLDEN,N.E.

    2007-07-23

    The International Organization for Standardization (ISO) has published a Guide to the expression of Uncertainty in Measurement (GUM). The IUPAC Commission on Isotopic Abundance and Atomic Weight (CIAAW) began attaching uncertainty limits to their recommended values about forty years ago. CIAAW's method for determining and assigning uncertainties has evolved over time. We trace this evolution to their present method and their effort to incorporate the basic ISO/GUM procedures into evaluations of these uncertainties. We discuss some dilemma the CIAAW faces in their present method and whether it is consistent with the application of the ISO/GUM rules. We discuss the attemptmore » to incorporate variations in measured isotope ratios, due to natural fractionation, into the ISO/GUM system. We make some observations about the inconsistent treatment in the incorporation of natural variations into recommended data and uncertainties. A recommendation for expressing atomic weight values using a tabulated range of values for various chemical elements is discussed.« less

  6. The Mean Life Squared Relationship for Abundances of Extinct Radioactivities

    NASA Technical Reports Server (NTRS)

    Lodders, K.; Cameron, A. G. W.

    2004-01-01

    We discovered that the abundances of now extinct radioactivities (relative to stable reference isotopes) in meteorites vary as a function of their mean lifetimes squared. This relationship applies to chondrites, achondrites, and irons but to calcium-aluminum inclusions (CAIs). Certain meteorites contain excesses in isotopic abundances from the decay of radioactive isotopes with half-lives much less than the age of the solar system. These short-lived radioactivities are now extinct, but they were alive when meteorites assembled in the early solar system. The origin of these radioactivities and the processes which control their abundances in the solar nebula are still not well understood. Some clues may come from our finding that the meteoritic abundances of now extinct radioactivities (relative to stable reference isotopes) vary as a function of their mean lifetimes squared. This relationship applies to chondrites, achondrites, and irons, but not to CAIs. This points to at least two different processes establishing the abundances of short-lived isotopes found in the meteoritic record.

  7. Hyperfine Induced Transitions as Diagnostics of Low Density Plasmas and Isotopic Abundance ratios.

    NASA Astrophysics Data System (ADS)

    Brage, T.; Judge, P. G.; Aboussaid, A.; Godefroid, M. R.; Jonsson, P.; Leckrone, D. S.

    1996-05-01

    We propose a new diagnostics of isotope abundance ratios and electron densities for low density plasmas, in the form of J = 0 -> J(') = 0 radiative transitions. These are usually viewed as being allowed only through two-photon decay, but they may also be induced by the hyperfine (HPF) interaction in atomic ions. This predicts a companion line to the E1] and M2 lines in the UV0.01 multiplet of ions isoelectronic to beryllium (e.g. C III, N IV, O V and Fe XXII) or magnesium (e.g. Si II, Ca IX, Fe XV and Ni XVII). As an example the companion line to the well known lambda lambda 1906.7,1908.7 lines in C III will be at 1909.597 Angstroms, but only present in the (13) C isotope (which has nuclear spin different from zero). We present new and accurate decay rates for the nsnp (3P^oJ) -> ns(2) (1S_{J('}=0)) transitions in ions of the Be (n=2) and Mg (n=3) isoelectronic sequences. We show that the HPF induced decay rates for the J = 0 -> J(') = 0 transitions are many orders of magnitude larger than those for the competing two-photon processes and, when present, are typically one or two orders of magnitude smaller than the decay rates of the magnetic quadrupole ( J = 2-> J(') = 0) transitions for these ions. We show that several of these HPF-induced transitions are of potential astrophysical interest, in ions of C, N, Na, Mg, Al, Si, K, Cr, Fe and Ni. We highlight those cases that may be of particular diagnostic value for determining isotopic abundance ratios and/or electron densities from UV or EUV emission line data. We present our atomic data in the form of scaling laws so that, given the isotopic nuclear spin and magnetic moment, a simple expression yields estimates for HPF induced decay rates. We examine some UV solar and nebular data in the light of these new results and suggest possible cases for future study. We could not find evidence for the existence of HPF induced lines in the spectra we examined, but we demonstrate that existing data have come close to providing

  8. A Computational Framework for High-Throughput Isotopic Natural Abundance Correction of Omics-Level Ultra-High Resolution FT-MS Datasets

    PubMed Central

    Carreer, William J.; Flight, Robert M.; Moseley, Hunter N. B.

    2013-01-01

    New metabolomics applications of ultra-high resolution and accuracy mass spectrometry can provide thousands of detectable isotopologues, with the number of potentially detectable isotopologues increasing exponentially with the number of stable isotopes used in newer isotope tracing methods like stable isotope-resolved metabolomics (SIRM) experiments. This huge increase in usable data requires software capable of correcting the large number of isotopologue peaks resulting from SIRM experiments in a timely manner. We describe the design of a new algorithm and software system capable of handling these high volumes of data, while including quality control methods for maintaining data quality. We validate this new algorithm against a previous single isotope correction algorithm in a two-step cross-validation. Next, we demonstrate the algorithm and correct for the effects of natural abundance for both 13C and 15N isotopes on a set of raw isotopologue intensities of UDP-N-acetyl-D-glucosamine derived from a 13C/15N-tracing experiment. Finally, we demonstrate the algorithm on a full omics-level dataset. PMID:24404440

  9. A novel method for collection of soil-emitted nitric oxide (NO) for natural abundance stable N isotope analysis

    NASA Astrophysics Data System (ADS)

    Yu, Z.; Elliott, E. M.

    2016-12-01

    The global inventory of NO emissions is poorly constrained with a large portion of the uncertainty attributed to soil NO emissions that result from soil abiotic and microbial processes. While natural abundance stable N isotopes (δ15N) in various soil N-containing compounds have proven to be a robust tracer of soil N cycling, soil δ15N-NO is rarely quantified mainly due to the diffuse nature, low concentrations, and high reactivity of soil-emitted NO. Here, we present the development and application of a dynamic flux chamber system capable of simultaneously measuring soil NO fluxes and collecting NO for δ15N-NO measurements. The system couples a widely used flow-through soil chamber with a NO collection train, in which NO can be converted to NO2 through O3 titration in a Teflon reaction coil, followed by NO2 collection in a 20% triethanolamine (TEA) solution as nitrite and nitrate for δ15N analysis using the denitrifier method. The efficiency of NO-NO2 conversion in the reaction coil and the recovery of NO in the TEA solution were determined experimentally and found to be quantitative (>99%) over a 10 to 749 ppbv NO mixing ratio range. An analytical NO tank (δ15N-NO=71.0±0.4‰) was used to calibrate the method for δ15N-NO analysis. The resulting accuracy and precision (1σ) of the method across various environmental conditions were 1.6‰ and 1.2‰, respectively. Using this new method, controlled laboratory incubations have been conducted to characterize NO emissions induced by rewetting of air-dried surface soil sampled from an urban forest. Pulsed NO emissions, up to 30 times higher than maximum soil NO emissions under steady state, were triggered upon the rewetting and lasted for next 36 hours. While the measured δ15N-NO over the course of the NO pulsing ranged from -52.0‰ and -34.6‰, reinforcing the notion that soil δ15N-NO is lower than those of fossil-fuel combustion sources, a transient δ15N-NO shift was captured immediately after the

  10. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

  11. Isotopic Analysis and Evolved Gases

    NASA Technical Reports Server (NTRS)

    Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

    1996-01-01

    Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

  12. High Relative Abundance of Biofuel Sourced Ethanol in Precipitation in the US and Brazil Determined Using Compound Specific Stable Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Shimizu, M. S.; Felix, J. D. D.; Casas, M.; Avery, G. B., Jr.; Kieber, R. J.; Mead, R. N.; Willey, J. D.; Lane, C.

    2017-12-01

    Ethanol biofuel production and consumption have increased exponentially over the last two decades to help reduce greenhouse gas emissions. Currently, 85% of global ethanol production and consumption occurs in the US and Brazil. Increasing biofuel ethanol usage in these two countries enhances emissions of uncombusted ethanol to the atmosphere contributing to poor air quality. Although measurements of ethanol in the air and the precipitation reveal elevated ethanol concentrations in densely populated cities, other sources such as natural vegetation can contribute to emission to the atmosphere. Previous modeling studies indicated up to 12% of atmospheric ethanol is from anthropogenic emissions. Only one gas phase study in southern Florida attempted to constrain the two sources through direct isotopic measurements. The current study used a stable carbon isotope method to constrain sources of ethanol in rainwater from the US and Brazil. A method was developed using solid phase microextraction (SPME) with subsequent analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Stable carbon isotope signatures (δ13C) of vehicle ethanol emission sources for both the US (-9.8‰) and Brazil (-12.7‰) represented C4 plants as feedstock (corn and sugarcane) for biofuel production. An isotope mixing model using biofuel from vehicles (C4 plants) and biogenic (C3 plants) end-members was implemented to estimate ethanol source apportionment in the rain. We found that stable carbon isotope ratio of ethanol in the rain ranged between -22.6‰ and -12.7‰. Our results suggest that the contribution of biofuel to atmospheric ethanol can be higher than previously estimated. As biofuel usage increasing globally, it is essential to determine the relative abundance of anthropogenic ethanol in other areas of the world.

  13. Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

    NASA Technical Reports Server (NTRS)

    Webster, Christopher R.; Mahaffy, Paul R.

    2011-01-01

    Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

  14. Anomalous 13C isotope abundances in C3S and C4H observed toward the cold interstellar cloud, Taurus Molecular Cloud-1.

    PubMed

    Sakai, Nami; Takano, Shuro; Sakai, Takeshi; Shiba, Shoichi; Sumiyoshi, Yoshihiro; Endo, Yasuki; Yamamoto, Satoshi

    2013-10-03

    We have studied the abundances of the (13)C isotopic species of C3S and C4H in the cold molecular cloud, Taurus Molecular Cloud-1 (Cyanopolyyne Peak), by radioastronomical observations of their rotational emission lines. The CCCS/(13)CCCS and CCCS/C(13)CCS ratios are determined to be >206 and 48 ± 15, respectively. The CC(13)CS line is identified with the aid of laboratory microwave spectroscopy, and the range of the CCCS/CC(13)CS ratio is found to be from 30 to 206. The abundances of at least two (13)C isotopic species of C3S are thus found to be different. Similarly, it is found that the abundances of the four (13)C isotopic species of C4H are not equivalent. The CCCCH/(13)CCCCH, CCCCH/C(13)CCCH, CCCCH/CC(13)CCH, and CCCCH/CCC(13)CH ratios are evaluated to be 141 ± 44, 97 ± 27, 82 ± 15, and 118 ± 23, respectively. Here the errors denote 3 times the standard deviation. These results will constrain the formation pathways of C3S and C4H, if the nonequivalence is caused during the formation processes of these molecules. The exchange reactions after the formation of these two molecules may also contribute to the nonequivalence. In addition, we have confirmed that the (12)C/(13)C ratio of some species are significantly higher than the interstellar elemental (12)C/(13)C ratio of 60-70. The observations of the (13)C isotopic species provide us with rich information on chemical processes in cold interstellar clouds.

  15. Direct uranium isotope ratio analysis of single micrometer-sized glass particles

    PubMed Central

    Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

    2012-01-01

    We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236U/238U isotope ratios (i.e. 10−5). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234U/238U and 235U/238U ratios. Experimental results obtained for 236U/238U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties Uc (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234U/238U, 235U/238U and 236U/238U, respectively. PMID:22595724

  16. Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

    PubMed

    Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

    2012-11-01

    We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. 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

  18. 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

  19. Preparative chromatography for specific δ13C isotopic analysis of individual carbohydrates in environmental samples

    NASA Astrophysics Data System (ADS)

    Nouara, Amel; Panagiotopoulos, Christos; Balesdent, Jérôme; Sempéré, Richard

    2017-04-01

    Carbohydrates are among the most abundant organic molecules on the Earth and are present in all geochemical systems. Despite their high abundance in the environment, very few studies assessed their origin using molecular carbohydrate isotopic analyses. In contrast with bulk stable isotope analysis (BSIA), which gives the isotopic signature of the entire sample without any specification about its chemical composition, compound specific 13C isotopic analysis of individual sugars (CSIA) offers valuable information about the origin of single molecules. Previous investigations used gas or liquid chromatography coupled with isotope ratio mass spectroscopy (GC-IRMS; HPLC-IRMS) for CSIA of sugars however the former requires δ13C corrections due to the carbon added to the sugar (derivatization) while the later does not provide always adequate separations among monosaccharides. Here we used cation preparative chromatography (Ca2+, Pb2+ and Na+) with refractive index detection in order to produce pure monosaccharide targets for subsequent EA-IRMS analyses. Milli-Q water was used as eluant at a flow rate 0.6 ml min-1. In general, three successive purifications (Ca2+, Pb2+, Ca2+) were sufficient to produce pure compounds. Pure monosaccharides were compared with authentic monosaccharide standards using 1H NMR and/or mass spectroscopy. The detection limit of our technique was about 1µM/sugar with a precision of 10% (n=6). Blanks run with Milli-Q water after three successive purifications resulted in carbon content of 0.13 to 2.77 µgC per collected sugar. These values are much lower than the minimum required amount (5 µgC) of the EA-IRSMS system with a precision of ± 0.35 ‰. Application of our method to environmental samples resulted in δ13C values of glucose, fructose, and levoglucosan in the range of -24 to -26 ‰ (PM10 atmospheric particles), and -15‰ to -22 ‰ for arabinose, glucose, and xylose (marine high molecular dissolved organic matter). These results fall in

  20. Application Of Stable Isotope Analysis To Study Temporal Changes In Foraging Ecology In A Highly Endangered Amphibian

    PubMed Central

    Gillespie, J. Hayley

    2013-01-01

    Background Understanding dietary trends for endangered species may be essential to assessing the effects of ecological disturbances such as habitat modification, species introductions or global climate change. Documenting temporal variation in prey selection may also be crucial for understanding population dynamics. However, the rarity, secretive behaviours and obscure microhabitats of some endangered species can make direct foraging observations difficult or impossible. Furthermore, the lethality or invasiveness of some traditional methods of dietary analysis (e.g. gut contents analysis, gastric lavage) makes them inappropriate for such species. Stable isotope analysis facilitates non-lethal, indirect analysis of animal diet that has unrealized potential in the conservation of endangered organisms, particularly amphibians. Methodology/findings I determined proportional contributions of aquatic macroinvertebrate prey to the diet of an endangered aquatic salamander Eurycea sosorum over a two-year period using stable isotope analysis of 13/12C and 15/14N and the Bayesian stable isotope mixing model SIAR. I calculated Strauss’ dietary electivity indices by comparing these proportions with changing relative abundance of potential prey species through time. Stable isotope analyses revealed that a previously unknown prey item (soft-bodied planarian flatworms in the genus Dugesia) made up the majority of E. sosorum diet. Results also demonstrate that E. sosorum is an opportunistic forager capable of diet switching to include a greater proportion of alternative prey when Dugesia populations decline. There is also evidence of intra-population dietary variation. Conclusions/significance Effective application of stable isotope analysis can help circumvent two key limitations commonly experienced by researchers of endangered species: the inability to directly observe these species in nature and the invasiveness or lethality of traditional methods of dietary analysis. This

  1. Stable isotope ratio analysis for authentication of lamb meat.

    PubMed

    Piasentier, E; Valusso, R; Camin, F; Versini, G

    2003-07-01

    The effectiveness of the analysis of stable isotope ratios ((13)C/(12)C and (15)N/(14)N) in fractions of lamb meat, measured by isotope ratio mass spectrometry, was evaluated as a method of feeding and geographical origin authentication. Analyses were carried out on meat from 12 lamb types, produced in couples in six European countries (country of origin, CO) and divided in three groups according to the feeding regime during their finishing period: suckled milk only, pasture without any solid supplementation and supplementation containing maize grain (feeding regime, FR). These analyses were made on two samples of longissimus thoracis muscle, taken from the 13th rib section of the left side of two different lambs, randomly chosen between the 120 selected to represent each lamb type. δ(13)C values varied significantly in different meat fractions, the difference being higher in protein than in fat (average difference 5.0‰). However, the pairs δ(13)C values of crude fat and protein were highly correlated (r=0.976) and affected by lamb type in a similar fashion, mainly reflecting animals' feeding regime. Even δ(15)N values of meat protein fraction showed significant differences between lamb types, not dependant on the feeding regime. In fact, lambs fed on similar diets, but in different countries, gave meat with different (15)N relative abundances. These findings provide the possibility of discriminating lamb types within the same feeding regime. Canonical discriminant analysis was carried out to evaluate whether lamb meat from different CO or FR or CO×FR interaction could be mathematically distinguished by its stable isotope ratios. On the basis of CO, the corrected empirical allocation of 79.2% of the initial observations and the corrected cross-validation of two thirds of the individual meat samples was obtained. FR gave better results: 91.7% of the individual meat samples was both correctly allocated and cross-validated, indicating the high potential of

  2. Stable Carbon Isotope Ratios of Individual Pollen Grains as a Proxy for C3- Versus C4-Grass Abundance in Paleorecords: A Validation Study

    NASA Astrophysics Data System (ADS)

    Nelson, D. M.; Hu, F.; Pearson, A.

    2007-12-01

    C3 and C4 grasses have distinct influences on major biogeochemical processes and unique responses to important environmental controls. Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. We recently developed a technique to analyze the stable carbon isotope composition of individual grass-pollen grains using a spooling- wire microcombustion device interfaced with an isotope-ratio mass spectrometer (Nelson et al. 2007). This technique holds promise for improving C3 and C4 grass reconstructions. It requires ~90% fewer grains than typical methods and avoids assumptions associated with mixing models. However, our previous work was based on known C3 and C4 grasses from herbarium specimens and field collections and the technique had not been test using geological samples. To test the ability of this technique to reproduce the abundance of C3 and C4 grasses on the landscape, we measured δ13C values of >1500 individual grains of grass pollen isolated from the surface sediments of 10 North American lakes that span a large gradient of C3 and C4 grass abundance. Results indicate a strong positive correlation (r=0.94) between % C4-grass pollen (derived from classifying δ13C values from single grains as C3 and C4) and the literature-reported abundance of C4 grasses on the landscape. However, the measured % C4-grass pollen shows some deviation from the actual abundance at sites with high proportions of C4 grasses. This is likely caused by uncertainty in the magnitude, composition, and variability of the analytical blank associated with these measurements. Correcting for this deviation using regression analysis improves the estimation of the abundance of C4 grasses on the landscape. Comparison of the % C4-grass pollen with C/N and δ13C measurements of total organic matter in the same lake-sediment samples illustrates the distinct advantage of grass-pollen δ13C as a proxy for

  3. Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.; Vogl, Jochen; Rosner, Martin; Prohaska, Thomas

    2014-01-01

    Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

  4. 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.

  5. Isotopic compositions of the elements 2013 (IUPAC Technical Report)

    USGS Publications Warehouse

    Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

    2016-01-01

    The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

  6. Isotopic determination of uranium in soil by laser induced breakdown spectroscopy

    DOE PAGES

    Chan, George C. -Y.; Choi, Inhee; Mao, Xianglei; ...

    2016-03-26

    Laser-induced breakdown spectroscopy (LIBS) operated under ambient pressure has been evaluated for isotopic analysis of uranium in real-world samples such as soil, with U concentrations in the single digit percentage levels. The study addresses the requirements for spectral decomposition of 235U and 238U atomic emission peaks that are only partially resolved. Although non-linear least-square fitting algorithms are typically able to locate the optimal combination of fitting parameters that best describes the experimental spectrum even when all fitting parameters are treated as free independent variables, the analytical results of such an unconstrained free-parameter approach are ambiguous. In this work, five spectralmore » decomposition algorithms were examined, with different known physical properties (e.g., isotopic splitting, hyperfine structure) of the spectral lines sequentially incorporated into the candidate algorithms as constraints. It was found that incorporation of such spectral-line constraints into the decomposition algorithm is essential for the best isotopic analysis. The isotopic abundance of 235U was determined from a simple two-component Lorentzian fit on the U II 424.437 nm spectral profile. For six replicate measurements, each with only fifteen laser shots, on a soil sample with U concentration at 1.1% w/w, the determined 235U isotopic abundance was (64.6 ± 4.8)%, and agreed well with the certified value of 64.4%. Another studied U line - U I 682.691 nm possesses hyperfine structure that is comparatively broad and at a significant fraction as the isotopic shift. Thus, 235U isotopic analysis with this U I line was performed with spectral decomposition involving individual hyperfine components. For the soil sample with 1.1% w/w U, the determined 235U isotopic abundance was (60.9 ± 2.0)%, which exhibited a relative bias about 6% from the certified value. The bias was attributed to the spectral resolution of our measurement system - the measured

  7. Partitioning nitrogen losses by natural abundance nitrogen isotope composition in a process-based statistical modelling framework

    NASA Astrophysics Data System (ADS)

    Dong, Ning; Wright, Ian; Prentice, Iain Colin

    2017-04-01

    Natural abundance of the stable isotope 15N is an under-utilized resource for research on the global terrestrial nitrogen cycle. Mass balance considerations suggest that if reactive N inputs have a roughly constant isotopic signature, soil δ15N should be mainly determined by the fraction of N losses by leaching - which barely discriminates against 15N - versus gaseous N losses, which discriminate strongly against 15N. We defined simple process-oriented functions of runoff (frunoff) and soil temperature (ftemp) and investigated the dependencies of soil and foliage δ15N (from global compilations of both types of measurement) on their ratio. Both plant and soil δ15N were found to systematically increase with ftemp/frunoff. Consistent with previous analyses, foliage δ15N was offset (more negative) with respect to soil δ15N, with significant differences in this offset between (from largest to smallest offset) ericoid, ectomycorrhizal, arbuscular mycorrhizal and non-mycorrhizal associated plants. δ15N values tend to be large and positive in the driest environments and to decline as frunoff increases, while also being lower in cold environments and increasing as ftemp increases. The fitted statistical model was used to estimate the gaseous fraction of total N losses from ecosystems (fgas) on a global grid basis. In common with earlier results, the largest values of fgas are predicted in the tropics and semi-arid subtropics. This analysis provides an indirectly estimated global mapping of fgas, which could be used as an improved benchmark for terrestrial nitrogen cycle models.

  8. Progress in the analysis and interpretation of N2O isotopes: Potential and future challenges

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Tuzson, Béla; Zellweger, Christoph; Harris, Eliza; Ibraim, Erkan; Yu, Longfei; Emmenegger, Lukas

    2017-04-01

    In recent years, research on nitrous oxide (N2O) stable isotopes has significantly advanced, addressing an increasing number of research questions in biogeochemical and atmospheric sciences [1]. An important milestone was the development of quantum cascade laser based spectroscopic devices [2], which are inherently specific for structural isomers (15N14N16O vs. 14N15N16O) and capable to collect real-time data with high temporal resolution, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. In combination with automated preconcentration, optical isotope ratio spectroscopy (OIRS) has been applied to disentangle source processes in suburban, rural and pristine environments [e.g. 3, 4]. Within the European Metrology Research Programme (EMRP) ENV52 project "Metrology for high-impact greenhouse gases (HIGHGAS)", the quality of N2O stable isotope analysis by OIRS, the comparability between laboratories, and the traceability to the international isotope ratio scales have been addressed. An inter-laboratory comparison between eleven IRMS and OIRS laboratories, organised within HIGHGAS, indicated limited comparability for 15N site preference, i.e. the difference between 15N abundance in central (N*NO) and end (*NNO) position [5]. In addition, the accuracy of the NH4NO3 decomposition reaction, which provides the link between 15N site preference and the international 15N/14N scale, was found to be limited by non-quantitative NH4NO3 decomposition in combination with substantially different isotope enrichment factors for both nitrogen atoms [6]. Results of the HIGHGAS project indicate that the following research tasks have to be completed to foster research on N2O isotopes: 1) develop improved techniques to link the 15N and 18O abundance and the 15N site preference in N2O to the international stable isotope ratio scales; 2) provide N2O reference materials, pure and diluted in an air matrix, to improve inter-laboratory compatibility. These tasks

  9. Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.

    1991-01-01

    Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

  10. Understanding Survival And Abundance Of Overwintering Warblers: Does Rainfall Matter?

    Treesearch

    Katie M. Dugger; John G Faaborg; Wayne J. Arendt; Keith A. Hobson

    2004-01-01

    We investigated relationships between warbler abundance and survival rates measured on a Puerto Rican wintering site and rainfall patterns measured on the wintering site and in regions where these warblers breed, as estimated using stable-isotope analysis (δD) of feathers collected from wintering birds. We banded birds using constant-effort mist netting...

  11. High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

    NASA Astrophysics Data System (ADS)

    Adamson, Kathryn; Candy, Ian; Whitfield, Liz

    2015-04-01

    Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows

  12. Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

    NASA Astrophysics Data System (ADS)

    Daeron, M.; Blamart, D.; Peral, M.; Affek, H. P.

    2016-12-01

    Conversion from raw IRMS data to clumped isotope anomalies in CO2 (Δ47) relies on four external parameters: the (13C/12C) ratio of VPDB, the (17O/16O) and (18O/16O) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (λ). Here we investigate the influence that these isotopic parameters exert on measured Δ47 values, using real-world data corresponding to 7 months of measurements; simulations based on randomly generated data; precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Δ47 values; reprocessing of two carbonate calibration data sets with different slopes of Δ47 versus T. Using different sets of isotopic parameters generally produces systematic offsets as large as 0.04 ‰ in final Δ47 values. What's more, even using a single set of isotopic parameters can produce intra- and inter-laboratory discrepancies in final Δ47 values, if some of these parameters are inaccurate. Depending on the isotopic compositions of the standards used for conversion to "absolute" values, these errors should correlate strongly with either δ13C or δ18O, or more weakly with both. Based on measurements of samples expected to display identical Δ47 values, such as 25°C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the isotopic parameters used so far in most clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards, which should be one of the key factors responsible for current inter-laboratory discrepancies. By contrast, the isotopic parameters of Brand et al. [2010] appear to yield accurate Δ47 values regardless of bulk isotopic composition. References:Brand, Assonov and Coplen [2010] http://dx.doi.org/10.1351/PAC-REP-09-01-05

  13. 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.

  14. Full-Spectrum-Analysis Isotope ID

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

    Mitchell, Dean J.; Harding, Lee; Thoreson, Gregory G.

    2017-06-28

    FSAIsotopeID analyzes gamma ray spectra to identify radioactive isotopes (radionuclides). The algorithm fits the entire spectrum with combinations of pre-computed templates for a comprehensive set of radionuclides with varying thicknesses and compositions of shielding materials. The isotope identification algorithm is suitable for the analysis of spectra collected by gamma-ray sensors ranging from medium-resolution detectors, such a NaI, to high-resolution detectors, such as HPGe. In addition to analyzing static measurements, the isotope identification algorithm is applied for the radiation search applications. The search subroutine maintains a running background spectrum that is passed to the isotope identification algorithm, and it also selectsmore » temporal integration periods that optimize the responsiveness and sensitivity. Gain stabilization is supported for both types of applications.« less

  15. Efficient Analysis of Mass Spectrometry Data Using the Isotope Wavelet

    NASA Astrophysics Data System (ADS)

    Hussong, Rene; Tholey, Andreas; Hildebrandt, Andreas

    2007-09-01

    Mass spectrometry (MS) has become today's de-facto standard for high-throughput analysis in proteomics research. Its applications range from toxicity analysis to MS-based diagnostics. Often, the time spent on the MS experiment itself is significantly less than the time necessary to interpret the measured signals, since the amount of data can easily exceed several gigabytes. In addition, automated analysis is hampered by baseline artifacts, chemical as well as electrical noise, and an irregular spacing of data points. Thus, filtering techniques originating from signal and image analysis are commonly employed to address these problems. Unfortunately, smoothing, base-line reduction, and in particular a resampling of data points can affect important characteristics of the experimental signal. To overcome these problems, we propose a new family of wavelet functions based on the isotope wavelet, which is hand-tailored for the analysis of mass spectrometry data. The resulting technique is theoretically well-founded and compares very well with standard peak picking tools, since it is highly robust against noise spoiling the data, but at the same time sufficiently sensitive to detect even low-abundant peptides.

  16. Applications of stable isotope analysis in mammalian ecology.

    PubMed

    Walter, W David; Kurle, Carolyn M; Hopkins, John B

    2014-01-01

    In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

  17. Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

    PubMed

    Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

    2013-03-01

    Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic

  18. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  19. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

    USGS Publications Warehouse

    Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua

    2013-01-01

    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  20. The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

    NASA Astrophysics Data System (ADS)

    Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

    2008-12-01

    The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results

  1. The chlorine isotope fingerprint of the lunar magma ocean.

    PubMed

    Boyce, Jeremy W; Treiman, Allan H; Guan, Yunbin; Ma, Chi; Eiler, John M; Gross, Juliane; Greenwood, James P; Stolper, Edward M

    2015-09-01

    The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because (37)Cl/(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, (37)Cl/(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high (37)Cl/(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon's history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

  2. High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

    PubMed Central

    Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

    2009-01-01

    A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

  3. ICL-based TDLAS sensor for real-time breath gas analysis of carbon monoxide isotopes.

    PubMed

    Ghorbani, Ramin; Schmidt, Florian M

    2017-05-29

    We present a compact sensor for carbon monoxide (CO) in air and exhaled breath based on a room temperature interband cascade laser (ICL) operating at 4.69 µm, a low-volume circular multipass cell and wavelength modulation absorption spectroscopy. A fringe-limited (1σ) sensitivity of 6.5 × 10 -8 cm -1 Hz -1/2 and a detection limit of 9 ± 5 ppbv at 0.07 s acquisition time are achieved, which constitutes a 25-fold improvement compared to direct absorption spectroscopy. Integration over 10 s increases the precision to 0.6 ppbv. The setup also allows measuring the stable isotope 13 CO in breath. We demonstrate quantification of indoor air CO and real-time detection of CO expirograms from healthy non-smokers and a healthy smoker before and after smoking. Isotope ratio analysis indicates depletion of 13 CO in breath compared to natural abundance.

  4. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    -rich ceria during re-oxidation at room temperature. The quantified oxygen isotope fractionation factors are consistent with the direct involvement of O2 in the rate limiting step for ceria reoxidation in air at room temperature. While additional parameters may reduce some of the uncertainties in our approach, this study demonstrates that isotope effects can be an encouraging tool for studying oxygen transport kinetics in ceria and other oxides. In addition, our finding warns of the special cares and limits in using ceria as an exchange medium for laboratory triple oxygen isotope analysis of CO2 or other oxygen-bearing gases.

  5. Coupled Mo-U abundances and isotopes in a small marine euxinic basin: Constraints on processes in euxinic basins

    NASA Astrophysics Data System (ADS)

    Bura-Nakić, Elvira; Andersen, Morten B.; Archer, Corey; de Souza, Gregory F.; Marguš, Marija; Vance, Derek

    2018-02-01

    Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (∼0.3‰ on 98Mo/95Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238U/235U fractionation of +0.6‰, in line with other studied euxinic

  6. A retro-biosynthetic approach to the prediction of biosynthetic pathways from position-specific isotope analysis as shown for tramadol

    PubMed Central

    Romek, Katarzyna M.; Nun, Pierrick; Remaud, Gérald S.; Silvestre, Virginie; Taïwe, Germain Sotoing; Lecerf-Schmidt, Florine; Boumendjel, Ahcène; De Waard, Michel; Robins, Richard J.

    2015-01-01

    Tramadol, previously only known as a synthetic analgesic, has now been found in the bark and wood of roots of the African medicinal tree Nauclea latifolia. At present, no direct evidence is available as to the biosynthetic pathway of its unusual skeleton. To provide guidance as to possible biosynthetic precursors, we have adopted a novel approach of retro-biosynthesis based on the position-specific distribution of isotopes in the extracted compound. Relatively recent developments in isotope ratio monitoring by 13C NMR spectrometry make possible the measurement of the nonstatistical position-specific natural abundance distribution of 13C (δ13Ci) within the molecule with better than 1‰ precision. Very substantial variation in the 13C positional distribution is found: between δ13Ci = −11 and −53‰. Distribution is not random and it is argued that the pattern observed can substantially be interpreted in relation to known causes of isotope fractionation in natural products. Thus, a plausible biosynthetic scheme based on sound biosynthetic principals of precursor–substrate relationships can be proposed. In addition, data obtained from the 18O/16O ratios in the oxygen atoms of the compound add support to the deductions made from the carbon isotope analysis. This paper shows how the use of 13C NMR at natural abundance can help with proposing a biosynthetic route to compounds newly found in nature or those difficult to tackle by conventional means. PMID:26106160

  7. IsoCor: correcting MS data in isotope labeling experiments.

    PubMed

    Millard, Pierre; Letisse, Fabien; Sokol, Serguei; Portais, Jean-Charles

    2012-05-01

    Mass spectrometry (MS) is widely used for isotopic labeling studies of metabolism and other biological processes. Quantitative applications-e.g. metabolic flux analysis-require tools to correct the raw MS data for the contribution of all naturally abundant isotopes. IsoCor is a software that allows such correction to be applied to any chemical species. Hence it can be used to exploit any isotopic tracer, from well-known ((13)C, (15)N, (18)O, etc) to unusual ((57)Fe, (77)Se, etc) isotopes. It also provides new features-e.g. correction for the isotopic purity of the tracer-to improve the accuracy of quantitative isotopic studies, and implements an efficient algorithm to process large datasets. Its user-friendly interface makes isotope labeling experiments more accessible to a wider biological community. IsoCor is distributed under OpenSource license at http://metasys.insa-toulouse.fr/software/isocor/

  8. The Application of Methane Clumped Isotope Measurements to Determine the Source of Large Methane Seeps in Alaskan Lakes

    NASA Astrophysics Data System (ADS)

    Douglas, P. M.; Stolper, D. A.; Eiler, J. M.; Sessions, A. L.; Walter Anthony, K. M.

    2014-12-01

    Natural methane emissions from the Arctic present an important potential feedback to global warming. Arctic methane emissions may come from either active microbial sources or from deep fossil reservoirs released by the thawing of permafrost and melting of glaciers. It is often difficult to distinguish between and quantify contributions from these methane sources based on stable isotope data. Analyses of methane clumped isotopes (isotopologues with two or more rare isotopes such as 13CH3D) can complement traditional stable isotope-based classifications of methane sources. This is because clumped isotope abundances (for isotopically equilibrated systems) are a function of temperature and can be used to identify pathways of methane generation. Additionally, distinctive effects of mixing on clumped isotope abundances make this analysis valuable for determining the origins of mixed gasses. We find large variability in clumped isotope compositions of methane from seeps in several lakes, including thermokarst lakes, across Alaska. At Lake Sukok in northern Alaska we observe the emission of dominantly thermogenic methane, with a formation temperature of at least 100° C. At several other lakes we find evidence for mixing between thermogenic methane and biogenic methane that forms in low-temperature isotopic equilibrium. For example, at Eyak Lake in southeastern Alaska, analysis of three methane samples results in a distinctive isotopic mixing line between a high-temperature end-member that formed between 100-170° C, and a biogenic end-member that formed in isotopic equilibrium between 0-20° C. In this respect, biogenic methane in these lakes resembles observations from marine gas seeps, oil degradation, and sub-surface aquifers. Interestingly, at Goldstream Lake in interior Alaska, methane with strongly depleted clumped-isotope abundances, indicative of disequilibrium gas formation, is found, similar to observations from methanogen culture experiments.

  9. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  10. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

    1990-01-01

    Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

  11. The chlorine isotope fingerprint of the lunar magma ocean

    PubMed Central

    Boyce, Jeremy W.; Treiman, Allan H.; Guan, Yunbin; Ma, Chi; Eiler, John M.; Gross, Juliane; Greenwood, James P.; Stolper, Edward M.

    2015-01-01

    The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free (“dry”) Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because 37Cl/35Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, 37Cl/35Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high 37Cl/35Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon’s history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets. PMID:26601265

  12. 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.

  13. CNO isotopes in red giant stars

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.

    1985-01-01

    Observational data on CNO abundance ratios in red giants and the interstellar medium (ISM) are analyzed for the implications for the production and distribution of CNO nuclides. The data included isotope abundance measurements for the atmospheres and recent ejecta of cool giants, e.g., carbon stars, S-type stars, red supergiants and oxygen-rich giants beginning an ascent of the giant branch. The contribution of intermediate-mass stars to galactic nuclear evolution is discussed after comparing red giant abundances with ISM abundances, particularly the isotopes O-16, -17 and -18. The O-12/O-18 ratios of red giants are distinctly different from those in interstellar molecular clouds. The CNO values also vary widely from the values found in the solar system.

  14. High-coverage quantitative proteomics using amine-specific isotopic labeling.

    PubMed

    Melanson, Jeremy E; Avery, Steven L; Pinto, Devanand M

    2006-08-01

    Peptide dimethylation with isotopically coded formaldehydes was evaluated as a potential alternative to techniques such as the iTRAQ method for comparative proteomics. The isotopic labeling strategy and custom-designed protein quantitation software were tested using protein standards and then applied to measure proteins levels associated with Alzheimer's disease (AD). The method provided high accuracy (10% error), precision (14% RSD) and coverage (70%) when applied to the analysis of a standard solution of BSA by LC-MS/MS. The technique was then applied to measure protein abundance levels in brain tissue afflicted with AD relative to normal brain tissue. 2-D LC-MS analysis identified 548 unique proteins (p<0.05). Of these, 349 were quantified with two or more peptides that met the statistical criteria used in this study. Several classes of proteins exhibited significant changes in abundance. For example, elevated levels of antioxidant proteins and decreased levels of mitochondrial electron transport proteins were observed. The results demonstrate the utility of the labeling method for high-throughput quantitative analysis.

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

    NASA Astrophysics Data System (ADS)

    Yeung, Laurence Y.

    2016-01-01

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

  16. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-29

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

  17. Documenting the diet in ancient human populations through stable isotope analysis of hair.

    PubMed Central

    Macko, S A; Engel, M H; Andrusevich, V; Lubec, G; O'Connell, T C; Hedges, R E

    1999-01-01

    Fundamental to the understanding of human history is the ability to make interpretations based on artefacts and other remains which are used to gather information about an ancient population. Sequestered in the organic matrices of these remains can be information, for example, concerning incidence of disease, genetic defects and diet. Stable isotopic compositions, especially those made on isolates of collagen from bones, have been used to help suggest principal dietary components. A significant problem in the use of collagen is its long-term stability, and the possibility of isotopic alteration during early diagenesis, or through contaminating condensation reactions. In this study, we suggest that a commonly overlooked material, human hair, may represent an ideal material to be used in addressing human diets of ancient civilizations. Through the analysis of the amino-acid composition of modern hair, as well as samples that were subjected to radiation (thus simulating ageing of the hair) and hair from humans that is up to 5200 years old, we have observed little in the way of chemical change. The principal amino acids observed in all of these samples are essentially identical in relative abundances and content. Dominating the compositions are serine, glutamic acid, threonine, glycine and leucine, respectively accounting for approximately 15%, 17%, 10%, 8% and 8% of the total hydrolysable amino acids. Even minor components (for example, alanine, valine, isoleucine) show similar constancy between the samples of different ages. This constancy clearly indicates minimal alteration of the amino-acid composition of the hair. Further, it would indicate that hair is well preserved and is amenable to isotopic analysis as a tool for distinguishing sources of nutrition. Based on this observation, we have isotopically characterized modern individuals for whom the diet has been documented. Both stable nitrogen and carbon isotope compositions were assessed, and together provide an

  18. Isotopic tracing of perchlorate in the environment

    USGS Publications Warehouse

    Sturchio, Neil C.; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Jackson, W. Andrew; Baskaran, Mark

    2012-01-01

    Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 −concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

  19. Abundance and isotopic composition of gases in the martian atmosphere from the Curiosity rover.

    PubMed

    Mahaffy, Paul R; Webster, Christopher R; Atreya, Sushil K; Franz, Heather; Wong, Michael; Conrad, Pamela G; Harpold, Dan; Jones, John J; Leshin, Laurie A; Manning, Heidi; Owen, Tobias; Pepin, Robert O; Squyres, Steven; Trainer, Melissa

    2013-07-19

    Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 ((40)Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10(-3); carbon monoxide, < 1.0 × 10(-3); and (40)Ar/(36)Ar, 1.9(±0.3) × 10(3). The (40)Ar/N2 ratio is 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The (40)Ar/(36)Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ(13)C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss.

  20. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    PubMed

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

    2009-06-01

    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  1. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

    NASA Astrophysics Data System (ADS)

    Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

    2018-06-01

    Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower

  2. Solar abundances as derived from solar energetic particles

    NASA Technical Reports Server (NTRS)

    Stone, E. C.

    1989-01-01

    Recent studies have shown that there are well defined average abundances of heavy (Z above 2) solar energetic particles (SEPs), with variations in the acceleration and propagation producing a systematic flare-to-flare fractionation that depends on the charge per unit mass of the ion. Correcting the average SEP abundances for this fractionation yields SEP-derived coronal abundances for 20 elements. High-resolution SEP studies have also provided isotopic abundances for five elements. SEP-derived abundances indicate that elements with high first ionization potentials (greater than 10 eV) are depleted in the corona relative to the photosphere and provide new information on the solar abundance of C and Ne-22.

  3. Extreme CO Isotopic Abundances in the ULIRG IRAS 13120-5453: An Extremely Young Starburst or Top-heavy Initial Mass Function

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

    Sliwa, Kazimierz; Wilson, Christine D.; Aalto, Susanne

    We present ALMA {sup 12}CO (J = 1-0, 3-2 and 6-5), {sup 13}CO (J = 1-0), and C{sup 18}O (J = 1-0) observations of the local ultraluminous infrared galaxy (ULIRG) IRAS 13120-5453. The morphologies of the three isotopic species differ, as {sup 13}CO shows a hole in emission toward the center. We measure integrated brightness temperature line ratios of {sup 12}CO/{sup 13}CO ≥ 60 (exceeding 200) and {sup 13}CO/C{sup 18}O ≤ 1 in the central region. Assuming optical thin emission, C{sup 18}O is more abundant than {sup 13}CO in several regions. The abundances within the central 500 pc are consistentmore » with the enrichment of the interstellar medium via a young starburst (<7 Myr), a top-heavy initial mass function, or a combination of both.« less

  4. Abundance, stable isotopic composition, and export fluxes of DOC, POC, and DIC from the Lower Mississippi River during 2006–2008

    USGS Publications Warehouse

    Cai, Yihua; Guo, Laodong; Wang, Xuri; Aiken, George R.

    2015-01-01

    Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006–2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge, while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg C yr−1 for DIC, 1.88 Tg C yr−1 for DOC, and 2.30 Tg C yr−1 for POC during 2006–2008. The discharge-normalized DIC yield decreased during wet seasons, while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge.

  5. Monsoon Variability In The Western Arabian Sea During Last 10,000 Years BP: A Planktic Foraminiferal Abundances And It's Stable Isotope Records

    NASA Astrophysics Data System (ADS)

    Singh, A. K.; Tiwari, M.; Sinha, D. K.; Ramesh, R.

    2007-12-01

    : The western Arabian Sea responds to the southwest monsoon winds by upwelling colder and nutrient rich waters from the deeper layers, causing a reduction in the sea surface temperature and enhanced biological productivity. A number of paleoclimatic studies have been carried out in this region to elucidate past monsoon variability (Sirocco et al., 1993; Gupta et al, 2003; Tiwari, 2005; Saher et.al.; 2007). Globigerina bulloides, a planktic foraminiferal species normally inhabiting surface ocean waters in temperate latitudes ( Be and Tolderlund , 1977) also becomes abundant at tropical latitudes upwelling occurs, and in these cases its abundance can exceed considerably. The conspicuous fluctuation in the abundance of Gg.bulloides during upwelling and non upwelling intervals is established through several studies ( Thiede and Junger, 1980, Gupta et al, 2003) This robust relation has been used as a proxy for wind velocity at several different times in the past in the Arabian Sea (Anderson et.al., 2002). A significant result from some of these centennially resolved Holocene records is declining abundance of Globigerina bulloides which is paralleled by reduced insolation record and this has been inferred as declining strength of Asian Monsoon. We are presenting here the data from the core SS4018 from near the Gulf of Aden, Western Arabian Sea taken at a water depth of 2830 m, precisely dated by the radiocarbon method using Accelerator Mass Spectrometry on planktonic foraminiferal separates. We have carried out the planktic foraminiferal census counts for each sample to know the relative abundance of key species. In addition to this, we have also employed multi- proxy approach such as oxygen and carbon isotopes of planktic foraminiferal tests, TOC, CaCO3 (%) to strengthen our interpretation and also to understand the relationships amongst the proxies themselves. Abundance of the key planktic foraminiferal species and other proxy records reveal at least 3 major climatic

  6. Lithium abundance and 6Li/7Li ratio in the active giant HD 123351. I. A comparative analysis of 3D and 1D NLTE line-profile fits

    NASA Astrophysics Data System (ADS)

    Mott, A.; Steffen, M.; Caffau, E.; Spada, F.; Strassmeier, K. G.

    2017-08-01

    Context. Current three-dimensional (3D) hydrodynamical model atmospheres together with detailed spectrum synthesis, accounting for departures from local thermodynamic equilibrium (LTE), permit to derive reliable atomic and isotopic chemical abundances from high-resolution stellar spectra. Not much is known about the presence of the fragile 6Li isotope in evolved solar-metallicity red giant branch (RGB) stars, not to mention its production in magnetically active targets like HD 123351. Aims: A detailed spectroscopic investigation of the lithium resonance doublet in HD 123351 in terms of both abundance and isotopic ratio is presented. From fits of the observed spectrum, taken at the Canada-France-Hawaii telescope, with synthetic line profiles based on 1D and 3D model atmospheres, we seek to estimate the abundance of the 6Li isotope and to place constraints on its origin. Methods: We derive the lithium abundance A(Li) and the 6Li/7Li isotopic ratio by fitting different synthetic spectra to the Li-line region of a high-resolution CFHT spectrum (R = 120 000, S/N = 400). The synthetic spectra are computed with four different line lists, using in parallel 3D hydrodynamical CO5BOLD and 1D LHD model atmospheres and treating the line formation of the lithium components in non-LTE (NLTE). The fitting procedure is repeated with different assumptions and wavelength ranges to obtain a reasonable estimate of the involved uncertainties. Results: We find A(Li) = 1.69 ± 0.11 dex and 6Li/7Li = 8.0 ± 4.4% in 3D-NLTE, using the line list of Meléndez et al. (2012, A&A, 543, A29), updated with new atomic data for V I, which results in the best fit of the lithium line profile of HD 123351. Two other line lists lead to similar results but with inferior fit qualities. Conclusions: Our 2σ detection of the 6Li isotope is the result of a careful statistical analysis and the visual inspection of each achieved fit. Since the presence of a significant amount of 6Li in the atmosphere of a cool

  7. Abundant Solar Nebula Solids in Comets

    NASA Technical Reports Server (NTRS)

    Messenger, S.; Keller, L. P.; Nakamura-Messenger, K.; Nguyen, A. N.; Clemett, S.

    2016-01-01

    Comets have been proposed to consist of unprocessed interstellar materials together with a variable amount of thermally annealed interstellar grains. Recent studies of cometary solids in the laboratory have shown that comets instead consist of a wide range of materials from across the protoplanetary disk, in addition to a minor complement of interstellar materials. These advances were made possible by the return of direct samples of comet 81P/Wild 2 coma dust by the NASA Stardust mission and recent advances in microscale analytical techniques. Isotopic studies of 'cometary' chondritic porous interplanetary dust particles (CP-IDPs) and comet 81P/Wild 2 Stardust samples show that preserved interstellar materials are more abundant in comets than in any class of meteorite. Identified interstellar materials include sub-micron-sized presolar silicates, oxides, and SiC dust grains and some fraction of the organic material that binds the samples together. Presolar grain abundances reach 1 weight percentage in the most stardust-rich CP-IDPs, 50 times greater than in meteorites. Yet, order of magnitude variations in presolar grain abundances among CP-IDPs suggest cometary solids experienced significant variations in the degree of processing in the solar nebula. Comets contain a surprisingly high abundance of nebular solids formed or altered at high temperatures. Comet 81P/Wild 2 samples include 10-40 micron-sized, refractory Ca- Al-rich inclusion (CAI)-, chondrule-, and ameboid olivine aggregate (AOA)-like materials. The O isotopic compositions of these refractory materials are remarkably similar to their meteoritic counterparts, ranging from 5 percent enrichments in (sup 16) O to near-terrestrial values. Comet 81P/Wild 2 and CP-IDPs also contain abundant Mg-Fe crystalline and amorphous silicates whose O isotopic compositions are also consistent with Solar System origins. Unlike meteorites, that are dominated by locally-produced materials, comets appear to be composed of

  8. High-resolution abundance analysis of HD 140283

    NASA Astrophysics Data System (ADS)

    Siqueira-Mello, C.; Andrievsky, S. M.; Barbuy, B.; Spite, M.; Spite, F.; Korotin, S. A.

    2015-12-01

    Context. HD 140283 is a reference subgiant that is metal poor and confirmed to be a very old star. The element abundances of this type of old star can constrain the nature and nucleosynthesis processes that occurred in its (even older) progenitors. The present study may shed light on nucleosynthesis processes yielding heavy elements early in the Galaxy. Aims: A detailed analysis of a high-quality spectrum is carried out, with the intent of providing a reference on stellar lines and abundances of a very old, metal-poor subgiant. We aim to derive abundances from most available and measurable spectral lines. Methods: The analysis is carried out using high-resolution (R = 81 000) and high signal-to-noise ratio (800 analysis in non-LTE (NLTE) is based on the MULTI code. We present LTE abundances for 26 elements, and NLTE calculations for the species C i, O i, Na i, Mg i, Al i, K i, Ca i, Sr ii, and Ba ii lines. Results: The abundance analysis provided an extensive line list suitable for metal-poor subgiant stars. The results for Li, CNO, α-, and iron peak elements are in good agreement with literature. The newly NLTE Ba abundance, along with a NLTE Eu correction and a 3D Ba correction from literature, leads to [Eu/Ba] = + 0.59 ± 0.18. This result confirms a dominant r-process contribution, possibly together with a very small contribution from the main s-process, to the neutron-capture elements in HD 140283. Overabundances of the lighter heavy elements and the high abundances derived for Ba, La, and Ce favour the operation of the weak r-process in HD 140283

  9. Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

    NASA Technical Reports Server (NTRS)

    Eigenbrode, Jennifer L.; Freeman, Katherine H.; Summons, Roger E.

    2007-01-01

    Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

  10. Trophic hierarchies revealed via amino acid isotopic analysis

    USDA-ARS?s Scientific Manuscript database

    Despite the potential of isotopic methods to illuminate trophic function, accurate estimates of lifetime feeding tendencies have remained elusive. A relatively new approach—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino ...

  11. 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.

  12. DETERMINING THE ELEMENTAL AND ISOTOPIC COMPOSITION OF THE PRESOLAR NEBULA FROM GENESIS DATA ANALYSIS: THE CASE OF OXYGEN.

    PubMed

    Laming, J Martin; Heber, V S; Burnett, D S; Guan, Y; Hervig, R; Huss, G R; Jurewicz, A J G; Koeman-Shields, E C; McKeegan, K D; Nittler, L; Reisenfeld, D B; Rieck, K D; Wang, J; Wiens, R C; Woolum, D S

    2017-12-10

    We compare element and isotopic fractionations measured in solar wind samples collected by NASA's Genesis mission with those predicted from models incorporating both the ponderomotive force in the chromosphere and conservation of the first adiabatic invariant in the low corona. Generally good agreement is found, suggesting that these factors are consistent with the process of solar wind fractionation. Based on bulk wind measurements, we also consider in more detail the isotopic and elemental abundances of O. We find mild support for an O abundance in the range 8.75 - 8.83, with a value as low as 8.69 disfavored. A stronger conclusion must await solar wind regime specific measurements from the Genesis samples.

  13. Long-term Records of Pacific Salmon Abundance From Sediment Core Analysis: Relationships to Past Climatic Change, and Implications for the Future

    NASA Astrophysics Data System (ADS)

    Finney, B.

    2002-12-01

    The response of Pacific salmon to future climatic change is uncertain, but will have large impacts on the economy, culture and ecology of the North Pacific Rim. Relationships between sockeye salmon populations and climatic change can be determined by analyzing sediment cores from lakes where sockeye return to spawn. Sockeye salmon return to their natal lake system to spawn and subsequently die following 2 - 3 years of feeding in the North Pacific Ocean. Sockeye salmon abundance can be reconstructed from stable nitrogen isotope analysis of lake sediment cores as returning sockeye transport significant quantities of N, relatively enriched in N-15, from the ocean to freshwater systems. Temporal changes in the input of salmon-derived N, and hence salmon abundance, can be quantified through downcore analysis of N isotopes. Reconstructions of sockeye salmon abundance from lakes in several regions of Alaska show similar temporal patterns, with variability occurring on decadal to millennial timescales. Over the past 2000 years, shifts in sockeye salmon abundance far exceed the historical decadal-scale variability. A decline occurred from about 100 BC - 800 AD, but salmon were consistently more abundant 1200 - 1900 AD. Declines since 1900 AD coincide with the period of extensive commercial fishing. Correspondence between these records and paleoclimatic data suggest that changes in salmon abundance are related to large scale climatic changes over the North Pacific. For example, the increase in salmon abundance c.a. 1200 AD corresponds to a period of glacial advance in southern Alaska, and a shift to drier conditions in western North America. Although the regionally coherent patterns in reconstructed salmon abundance are consistent with the hypothesis that climate is an important driver, the relationships do not always follow patterns observed in the 20th century. A main feature of recorded climate variability in this region is the alternation between multi-decade periods of

  14. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, Ben D.; Sturchio, Neil C.

    1999-01-01

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO.sub.2 and CuCl. The CO.sub.2 is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH.sub.3 I to form CH.sub.3 Cl, extracted and analyzed for chlorine isotope ratio.

  15. Rapidly assessing changes in bone mineral balance using natural stable calcium isotopes

    PubMed Central

    Morgan, Jennifer L. L.; Skulan, Joseph L.; Gordon, Gwyneth W.; Romaniello, Stephen J.; Smith, Scott M.; Anbar, Ariel D.

    2012-01-01

    The ability to rapidly detect changes in bone mineral balance (BMB) would be of great value in the early diagnosis and evaluation of therapies for metabolic bone diseases such as osteoporosis and some cancers. However, measurements of BMB are hampered by difficulties with using biochemical markers to quantify the relative rates of bone resorption and formation and the need to wait months to years for altered BMB to produce changes in bone mineral density large enough to resolve by X-ray densitometry. We show here that, in humans, the natural abundances of Ca isotopes in urine change rapidly in response to changes in BMB. In a bed rest experiment, use of high-precision isotope ratio MS allowed the onset of bone loss to be detected in Ca isotope data after about 1 wk, long before bone mineral density has changed enough to be detectable with densitometry. The physiological basis of the relationship between Ca isotopes and BMB is sufficiently understood to allow quantitative translation of changes in Ca isotope abundances to changes in bone mineral density using a simple model. The rate of change of bone mineral density inferred from Ca isotopes is consistent with the rate observed by densitometry in long-term bed rest studies. Ca isotopic analysis provides a powerful way to monitor bone loss, potentially making it possible to diagnose metabolic bone disease and track the impact of treatments more effectively than is currently possible. PMID:22652567

  16. Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

    NASA Astrophysics Data System (ADS)

    Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

    2016-04-01

    An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (< 0.1 ‰) measurements in ambient air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B

  17. Advances in Multicollector ICPMS for precise and accurate isotope ratio measurements of Uranium isotopes

    NASA Astrophysics Data System (ADS)

    Bouman, C.; Lloyd, N. S.; Schwieters, J.

    2011-12-01

    The accurate and precise determination of uranium isotopes is challenging, because of the large dynamic range posed by the U isotope abundances and the limited available sample material. Various mass spectrometric techniques are used for the measurement of U isotopes, where TIMS is the most accepted and accurate one. Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) can offer higher productivity compared to TIMS, but is traditionally limited by low efficiency of sample utilisation. This contribution will discuss progress in MC-ICPMS for detecting 234U, 235U, 236U and 238U in various uranium reference materials from IRMM and NBL. The Thermo Scientific NEPTUNE Plus with Jet Interface offers a modified dry plasma ICP interface using a large interface pump combined with a special set of sample and skimmer cones giving ultimate sensitivity for all elements across the mass range. For uranium, an ion yield of > 3 % was reported previously [1]. The NEPTUNE Plus also offers Multi Ion Counting using discrete dynode electron multipliers as well as two high abundance-sensitivity filters to discriminate against peak tailing effects on 234U and 236U originating from the major uranium beams. These improvements in sensitivity and dynamic range allow accurate measurements of 234U, 235U and 236U abundances on very small samples and at low concentration. In our approach, minor U isotopes 234U and 236U were detected on ion counters with high abundance sensitivity filters, whereas 235U and 238U were detected on Faraday Cups using a high gain current amplifier (10e12 Ohm) for 235U. Precisions and accuracies for 234U and 236U were down to ~1%. For 235U, subpermil levels were reached.

  18. Light stable isotope analysis of meteorites by ion microprobe

    NASA Technical Reports Server (NTRS)

    Mcsween, Harry Y., Jr.

    1994-01-01

    The main goal was to develop the necessary secondary ion mass spectrometer (SIMS) techniques to use a Cameca ims-4f ion microprobe to measure light stable isotope ratios (H, C, O and S) in situ and in non-conducting mineral phases. The intended application of these techniques was the analysis of meteorite samples, although the techniques that have been developed are equally applicable to the investigation of terrestrial samples. The first year established techniques for the analysis of O isotope ratios (delta O-18 and delta O-17) in conducting mineral phases and the measurement of S isotope ratios (delta S-34) in a variety of sulphide phases. In addition, a technique was developed to measure delta S-34 values in sulphates, which are insulators. Other research undertaken in the first year resulted in SIMS techniques for the measurement of wide variety of trace elements in carbonate minerals, with the aim of understanding the nature of alteration fluids in carbonaceous chondrites. In the second year we developed techniques for analyzing O isotope ratios in nonconducting mineral phases. These methods are potentially applicable to the measurement of other light stable isotopes such as H, C and S in insulators. Also, we have further explored the analytical techniques used for the analysis of S isotopes in sulphides by analyzing troilite in a number of L and H ordinary chondrites. This was done to see if there was any systematic differences with petrological type.

  19. ICC-CLASS: isotopically-coded cleavable crosslinking analysis software suite

    PubMed Central

    2010-01-01

    Background Successful application of crosslinking combined with mass spectrometry for studying proteins and protein complexes requires specifically-designed crosslinking reagents, experimental techniques, and data analysis software. Using isotopically-coded ("heavy and light") versions of the crosslinker and cleavable crosslinking reagents is analytically advantageous for mass spectrometric applications and provides a "handle" that can be used to distinguish crosslinked peptides of different types, and to increase the confidence of the identification of the crosslinks. Results Here, we describe a program suite designed for the analysis of mass spectrometric data obtained with isotopically-coded cleavable crosslinkers. The suite contains three programs called: DX, DXDX, and DXMSMS. DX searches the mass spectra for the presence of ion signal doublets resulting from the light and heavy isotopic forms of the isotopically-coded crosslinking reagent used. DXDX searches for possible mass matches between cleaved and uncleaved isotopically-coded crosslinks based on the established chemistry of the cleavage reaction for a given crosslinking reagent. DXMSMS assigns the crosslinks to the known protein sequences, based on the isotopically-coded and un-coded MS/MS fragmentation data of uncleaved and cleaved peptide crosslinks. Conclusion The combination of these three programs, which are tailored to the analytical features of the specific isotopically-coded cleavable crosslinking reagents used, represents a powerful software tool for automated high-accuracy peptide crosslink identification. See: http://www.creativemolecules.com/CM_Software.htm PMID:20109223

  20. Stable Isotope Analysis of Chlorate

    NASA Astrophysics Data System (ADS)

    Brundrett, M.; Jackson, W. A.; Sturchio, N. C.; Bohlke, J. K.; Hatzinger, P.

    2016-12-01

    Studies have confirmed the presence of chlorate (ClO3-) throughout terrestrial and extraterrestrial systems generally in excess of perchlorate (ClO4-) [1, 2]. ClO3- occurrence, production, and post depositional transformation has significant implications to our understanding of atmospheric Cl cycling and potential biogeochemical reactions on Earth and Mars. The isotopic composition of oxyanions can be used to evaluate their production mechanisms and post-depositional alteration [3, 4]. However, no information is available on the natural isotopic composition of ClO3-. The objective of this study was to develop a method to measure the stable isotope composition (δ18O, δ17O and δ37Cl) of ClO3- and to determine the isotopic composition of ClO3- in natural desert salt accumulations that have been studied previously for NO3- and ClO4- isotopic composition. The process of ClO3- purification and analysis of δ18O, δ 17O and δ37Cl is problematic but has recently been resolved by adapting previously published methods for ClO4-. Competitive anions (e.g. NO3-, Cl-, ClO4-, and SO4-2) are removed through a series of processes including biological reduction, solid phase extraction, and anion or cation exchange. Initial results for control samples treated with the above method have a maximum variation of ± 2 ‰. These methods are being applied to representative samples to determine if various sources of natural and synthetic ClO3- have distinctive isotopic compositions, as reported previously for ClO4- [3, 4]. Establishing the range of isotopic composition of natural ClO3- also could provide information about atmospheric ClO3- production mechanisms and post-depositional processing, with implications for the atmospheric chemistry of oxychlorine compounds and the global biogeochemical cycling of Cl. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Bao and Gu (2004) ES&T 38, 5073-5077.

  1. Method for isotopic analysis of chlorinated organic compounds

    DOEpatents

    Holt, B.D.; Sturchio, N.C.

    1999-08-24

    The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO{sub 2} and CuCl. The CO{sub 2} is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH{sub 3}I to form CH{sub 3}Cl, extracted and analyzed for chlorine isotope ratio. 9 figs.

  2. 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.

  3. An abundance analysis of Tau Herculis, B5 IV

    NASA Technical Reports Server (NTRS)

    Adelman, S. J.

    1977-01-01

    An abundance analysis of the sharp-lined star Tau Herculis (B5 IV) has been performed using a fully line-blanketed model atmosphere. The derived abundances are similar to those of the sun and the normal main-sequence B stars Iota Her (B3 V) and Nu Cap (B9 V).

  4. Environmental and biomedical applications of natural metal stable isotope variations

    USGS Publications Warehouse

    Bullen, T.D.; Walczyk, T.

    2009-01-01

    etal stable isotopes are now being used to trace metal contaminants in the environment and as indicators of human systemic function where metals play a role. Stable isotope abundance variations provide information about metal sources and the processes affecting metals in complex natural systems, complementing information gained from surrogate tracers, such as metal abundance ratios or biochemical markers of metal metabolism. The science is still in its infancy, but the results of initial studies confirm that metal stable isotopes can provide a powerful tool for forensic and biomedical investigations.

  5. Holocene Paleohydrological Changes in Northern Michigan: Interpretations of Biomarker Distributions and Compound Specific Stable Isotope Analysis from Peatlands

    NASA Astrophysics Data System (ADS)

    Nichols, J. E.; Booth, R. K.; Jackson, S. T.; Pendall, E. G.; Huang, Y.

    2006-12-01

    Sediments of ombrotrophic peatlands are excellent archives for reconstructing past changes in precipitation/evaporation (P/E) balance. Multiproxy analysis of these sediments is critical for better understanding of climatic events experienced by these highly sensitive systems, as each proxy may respond to different climate parameters. In this study, we use distributions of n-alkanes and δD of Sphagnum biomarkers to interpret paleohydrology from sediments of Irwin Smith Bog, northern Michigan. We then integrate these data with pollen data and testate amoebae-inferred water table depth. Sphagnum moss is the dominant peat former in ombrotrophic bogs, but vascular plants become abundant when water tables are drawn down. Thus, the abundance of Sphagnum relative to vascular plants is indicative of peatland hydrology. The n-alkanes produced by Sphagnum differ from vascular plants in the relative abundance of the different homologues, with the former having excess amounts of shorter chain C23 n-alkane. We use several measures (compound ratios, PCA) to show changes in then-alkane distributions in the sediments, and thus changes in the peatland plant community. Our data provide high- resolution, quantitative paleohydrological records for the study region that are consistent with other records. We also show that the relative abundance of a newly identified Sphagnum biomarker, 2-heptacosanone, can be used to reconstruct changing plant communities. Because ombrotrophic systems lose water by evaporation, drier/warmer conditions cause hydrogen isotopic enrichment of bog water and Sphagnum biomarkers. We measured the δD of C23 n-alkane and 2-heptacosanone to provide additional paleoclimate information. Our multiproxy approach allows us to better understand the climate changes during key intervals of the Holocene. For example, a sharp decrease in the abundance of Tsuga canadensis (hemlock) pollen has been previously identified in records from many places throughout eastern North

  6. The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1981-01-01

    The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

  7. Stable isotope analysis of energy dynamics in aquatic ecosystems suggests trophic shifts following severe wildfire

    NASA Astrophysics Data System (ADS)

    Martens, A. M.; Silins, U.; Bladon, K. D.; Williams, C.; Wagner, M. J.; Luchkow, E.

    2015-12-01

    Wildfire alters landscapes and can have significant impacts on stream ecosystems. The 2003 Lost Creek wildfire was one of the most severe on Alberta's eastern rocky mountain slopes, resulting in elevated sediment production and nutrient (phosphorus, nitrogen, and carbon) export in impacted streams. These resulted in increased algal productivity and macroinvertebrate abundance and diversity, and as a result, fish in watersheds draining wildfire affected catchments were larger than those in the same age class from reference (unburned) watersheds. In the present investigation, stable isotope analysis of C and N was utilized to evaluate ecosystem energy dynamics and describe trophic relationships in those watersheds. Aquatic invertebrates from burned catchments showed enrichment in δ13C and δ15N relative to algae suggesting a reliance on algae (autochthony) as a primary source of energy. Invertebrates from unburned systems were depleted in δ13C relative to algae indicating reliance on allochthonous or terrestrial primary energy sources. Preliminary analysis of δ15N in macroinvertebrates showed slight enrichment in burned catchments suggesting a trophic shift. More comprehensive macroinvertebrate sampling and identification has been conducted; isotopic analysis will provide greater resolution of how specific families within feeding guilds have been affected by wildfire. This will provide more robust insights into how wildfires may impact stream ecology in mountain environments.

  8. Helium and Carbon Isotope and Relative Abundance Relationships in Lau Basin Basalts: Resolving Mantle Source Composition from Degassing and Contamination Effects

    NASA Astrophysics Data System (ADS)

    Vukajlovich, D. J.; Hilton, D. R.; Castillo, P. R.; Hawkins, J. W.

    2005-12-01

    The Lau Basin has multiple mantle source components including contributions from the Indian and Pacific MORB sources, Tonga-Kermadec Arc and Samoan plume. In order to characterize the volatile systematics of these various sources and to map their spatial distribution, we have sampled basaltic glasses from over 50 dredge sites covering all known spreading centers in the basin as well as many off-axis seamounts. Here, we report He abundance and isotope results obtained by crushing, in addition to CO2 released through stepped heating, from sites at the Mangatolu Triple Junction (MTJ), Rochambeau Bank (RB), Peggy Ridge, and the Northern, Eastern and Central Lau Spreading Centers. High 3He/4He ratios from RB (up to 23 RA, where RA = air 3He/4He) confirm the presence of a plume component in the northwestern Lau Basin (Poreda, EPSL, 1985). Central and Eastern Lau Spreading Center basalts have 3He/4He ratios between 8.3 and 9.4 RA, consistent with a depleted, MORB-like mantle source with little influence from slab or crustal helium. In contrast, the large range in helium isotope ratios of MTJ samples (0.85 to 7.9 RA) and the correlation between low He abundances (~2 - 3 × 10-9 cm3/g) and low helium isotope ratios suggests the volatiles in this region have been severely affected by degassing and additions of radiogenic (crustal) He. CO2 abundances and carbon isotopes for samples from RB vary from 70 to 119 ppm ([CO2]total) with δ13Cvesicle falling between -12.3 to -14.8 ‰ and δ13Cdissolved lying between -9.3 to -10.7 ‰. In the MTJ, low helium concentration samples have δ13C as low as -27.4 ‰ and [CO2]total as low as 7.6ppm; interestingly, this region also has samples with the highest measured values (up to -6.3 ‰ and 132ppm total C). Combining the carbon and helium data, CO2/3He ratios in the MTJ range from arc-like values (~1010) to sediment or crustal values (~1013) showing the superimposition of degassing and/or contamination effects on a predominant slab

  9. Origin and abundance of water in carbonaceous asteroids

    NASA Astrophysics Data System (ADS)

    Marrocchi, Yves; Bekaert, David V.; Piani, Laurette

    2018-01-01

    The origin and abundance of water accreted by carbonaceous asteroids remains underconstrained, but would provide important information on the dynamic of the protoplanetary disk. Here we report the in situ oxygen isotopic compositions of aqueously formed fayalite grains in the Kaba and Mokoia CV chondrites. CV chondrite bulk, matrix and fayalite O-isotopic compositions define the mass-independent continuous trend (δ17O = 0.84 ± 0.03 × δ18O - 4.25 ± 0.1), which shows that the main process controlling the O-isotopic composition of the CV chondrite parent body is related to isotopic exchange between 16O-rich anhydrous silicates and 17O- and 18O-rich fluid. Similar isotopic behaviors observed in CM, CR and CO chondrites demonstrate the ubiquitous nature of O-isotopic exchange as the main physical process in establishing the O-isotopic features of carbonaceous chondrites, regardless of their alteration degree. Based on these results, we developed a new approach to estimate the abundance of water accreted by carbonaceous chondrites (quantified by the water/rock ratio) with CM (0.3-0.4) ≥ CR (0.1-0.4) ≥ CV (0.1-0.2) > CO (0.01-0.10). The low water/rock ratios and the O-isotopic characteristics of secondary minerals in carbonaceous chondrites indicate they (i) formed in the main asteroid belt and (ii) accreted a locally derived (inner Solar System) water formed near the snowline by condensation from the gas phase. Such results imply low influx of D- and 17O- and 18O-rich water ice grains from the outer part of the Solar System. The latter is likely due to the presence of a Jupiter-induced gap in the protoplanetary disk that limited the inward drift of outer Solar System material at the exception of particles with size lower than 150 μm such as presolar grains. Among carbonaceous chondrites, CV chondrites show O-isotopic features suggesting potential contribution of 17-18O-rich water that may be related to their older accretion relative to other hydrated

  10. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    NASA Technical Reports Server (NTRS)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  11. 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.

  12. Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

    PubMed

    Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

    2015-01-01

    This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

  13. Initial results from the Caltech/DRSI balloon-borne isotope experiment

    NASA Technical Reports Server (NTRS)

    Schindler, S. M.; Buffington, A.; Christian, E. C.; Grove, J. E.; Lau, K. H.; Stone, E. C.; Rasmussen, I. L.; Laursen, S.

    1985-01-01

    The Caltech/DSRI balloonborne High Energy Isotope Spectrometer Telescope (HEIST) was flown successfully from Palestine, Texas on 14 May, 1984. The experiment was designed to measure cosmic ray isotopic abundances from neon through iron, with incident particle energies from approx. 1.5 to 2.2 GeV/nucleon depending on the element. During approximately 38 hours at float altitude, 100,000 events were recorded with Z or = 6 and incident energies approx. 1.5 GeV/nucleon. We present results from the ongoing data analysis associated with both the preflight Bevalac calibration and the flight data.

  14. Initial results from the Caltech/DSRI balloon-borne isotope experiment

    NASA Technical Reports Server (NTRS)

    Schindler, S. M.; Buffington, A.; Christian, E. C.; Grove, J. E.; Lau, K. H.; Stone, E. C.; Rasmussen, I. L.; Laursen, S.

    1985-01-01

    The Caltech/DSRI balloon-borne High Energy Isotope Spectrometer Telescope (HEIST) was flown successfully from Palestine, Texas on 14 May 1984. The experiment was designed to measure cosmic ray isotopic abundances from neon through iron, with incident particle energies from approximately 1.5 to 2.2 GeV/nucleon, depending on the element. During approximately 38 hours at float altitude, 10 to the 5th events were recorded with Z or = 6 and incident energies 1.5 GeV/nucleon. We present results from the ongoing data analysis associated with both the pre-flight Bevalac calibration and the flight data.

  15. CNO isotopes in red giant stars

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.

    1985-01-01

    The production and distribution of the CNO nuclides is discussed in light of observed abundance ratios in red giants and in the interstellar medium. Isotope abundances have been measured in the atmospheres and in the recent ejecta of cool giants, including carbon stars, S-type stars and red supergiants as well as in oxygen-rich giants making their first ascent of the giant branch. Several of the observations suggest revision of currently accepted nuclear cross-sections and of the mixing processes operating in giant envelopes. By comparing red giant abundances with high-quality observations of the interstellar medium, conclusions are reached about the contribution of intermediate-mass stars to galactic nuclear evolution. The three oxygen isotopes, O-16, -17 and -18, are particularly valuable for such comparison because they reflect three different stages of stellar nucleosynthesis. One remarkable result comes from observations of O-17/O-18 in several classes of red giant stars. The observed range of values for red giants excludes the entire range of values seen in interstellar molecular clouds. Furthermore, both the observations of stars and interstellar clouds exclude the isotopic ratio found in the solar system.

  16. Carbon isotope geochemistry and geobiology

    NASA Technical Reports Server (NTRS)

    Desmarais, D.

    1985-01-01

    Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

  17. Developing SNMS for Full-Spectrum High-Sensitivity In-Situ Isotopic Analysis of Individual Comet Grains Collected by Stardust?

    NASA Technical Reports Server (NTRS)

    Chen, Chun-Yen; Shen, Jason Jiun-San; Lee, Typhoon; Calaway, Wallis; Veryovkin, Igor; Moore, Jerry; Pellin, Michael

    2005-01-01

    In anticipation of the return of comet (and ISM?) dust grains by the Stardust mission [1] in mid-January next year, Academia Sinica (AS) and Argonne National Laboratory (ANL) have entered into a collaboration to develop instrument and method for the isotopic analysis of these samples. We need to achieve the highest possible sensitivity so that we can analyze individual grains one at a time to the smallest possible size. Only by doing so can we hope to reach one of the main science goals of the mission, namely the recognition of those isotopically distinct grains each carrying the characteristic signature of a particular nucleosynthetic stage of its parent star. In order to facilitate the interpretation of these grains the second requirement of our method is that the measurements must be made over the widest possible mass range before samples exhaustion. For instance, the thermonuclear fusion reactions that produced the isotopes of various major elements of a wide mass range required drastically different temperatures. Therefore their abundances could constrain the conditions at greatly varying depth inside the source star hence its structure and evolution.

  18. Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

    USGS Publications Warehouse

    Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

    1978-01-01

    Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

  19. Natural abundance N stable isotopes in plants and soils as an indicator of N deposition hotspots in urban environments

    NASA Astrophysics Data System (ADS)

    Trammell, T. L.

    2017-12-01

    The natural abundance of stable isotopes in plants and soils has been utilized to understand ecological phenomenon. Foliar δ15N is an integrator of soil δ15N, atmospheric N sources, and fractionation processes that occur during plant N uptake, plant N assimilation, and mycorrhizal associations. The amount of reactive N in the environment has greatly increased due to human activities, and urban ecosystems experience excess N deposition that can have cascading effects on plants and soils. Foliar δ15N has been shown to increase with increasing N deposition and nitrification rates suggesting increased foliar δ15N occurs with greater N inputs as a result of accelerated soil N cycling. Thus, foliar δ15N can be an indication of soil N availability for plant uptake and soil N cycling rates, since high N availability results in increased soil N cycling and subsequent loss of 14N. Limited research has utilized foliar and soil δ15N in urban forests to assess the importance of plant uptake of atmospheric N deposition and to gain insight about ecosystem processes. Previous investigations found foliar δ15N of mature trees in urban forests is not only related to elevated pollutant-derived N deposition, but also to soil N availability and soil N cycling rates. Similarly, enriched foliar δ15N of urban saplings was attributed to soil characteristics that indicated higher nitrification, thus, greater nitrate leaching and low N retention in the urban soils. These studies demonstrate the need for measuring the δ15N of various plant and soil N sources while simultaneously measuring soil N processes (e.g., net nitrification rates) in order to use natural abundance δ15N of plants and soils to assess N sources and cycling in urban forests. A conceptual framework that illustrates biogenic and anthropogenic controls on nitrogen isotope composition in urban plants and soils will be presented along with foliar and soil δ15N from urban forests across several cities as a proof of

  20. Application of stable isotope tools for evaluating natural and stimulated biodegradation of organic pollutants in field studies.

    PubMed

    Fischer, Anko; Manefield, Mike; Bombach, Petra

    2016-10-01

    Stable isotope tools are increasingly applied for in-depth evaluation of biodegradation of organic pollutants at contaminated field sites. They can be divided into three methods i) determination of changes in natural abundance of stable isotopes using compound-specific stable isotope analysis (CSIA), ii) detection of incorporation of stable-isotope label from a stable-isotope labelled target compound into degradation and/or mineralisation products and iii) determination of stable-isotope label incorporation into biomarkers using stable isotope probing (SIP). Stable isotope tools have been applied as key monitoring tools for multiple-line-of-evidence-approaches (MLEA) for sensitive evaluation of pollutant biodegradation. This review highlights the application of CSIA, SIP and MLEA including stable isotope tools for assessing natural and stimulated biodegradation of organic pollutants in field studies dealing with soil and groundwater contaminations. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Determining the Elemental and Isotopic Composition of the Pre-solar Nebula from Genesis Data Analysis: The Case of Oxygen

    DOE PAGES

    Laming, J. Martin; Heber, Veronika S.; Burnett, Donald S.; ...

    2017-12-06

    Here, we compare element and isotopic fractionations measured in bulk solar wind samples collected by NASA's Genesis mission with those predicted from models incorporating both the ponderomotive force in the chromosphere and conservation of the first adiabatic invariant in the low corona. Generally good agreement is found, suggesting that these factors are consistent with the process of solar wind fractionation. Based on bulk wind measurements, we also consider in more detail the isotopic and elemental abundances of O. We also find mild support for an O abundance in the range 8.75–8.83, with a value as low as 8.69 disfavored. Amore » stronger conclusion must await solar wind regime-specific measurements from the Genesis samples.« less

  2. Determining the Elemental and Isotopic Composition of the Pre-solar Nebula from Genesis Data Analysis: The Case of Oxygen

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

    Laming, J. Martin; Heber, Veronika S.; Burnett, Donald S.

    Here, we compare element and isotopic fractionations measured in bulk solar wind samples collected by NASA's Genesis mission with those predicted from models incorporating both the ponderomotive force in the chromosphere and conservation of the first adiabatic invariant in the low corona. Generally good agreement is found, suggesting that these factors are consistent with the process of solar wind fractionation. Based on bulk wind measurements, we also consider in more detail the isotopic and elemental abundances of O. We also find mild support for an O abundance in the range 8.75–8.83, with a value as low as 8.69 disfavored. Amore » stronger conclusion must await solar wind regime-specific measurements from the Genesis samples.« less

  3. Organic vs. conventional grassland management: do (15)N and (13)C isotopic signatures of hay and soil samples differ?

    PubMed

    Klaus, Valentin H; Hölzel, Norbert; Prati, Daniel; Schmitt, Barbara; Schöning, Ingo; Schrumpf, Marion; Fischer, Markus; Kleinebecker, Till

    2013-01-01

    Distinguishing organic and conventional products is a major issue of food security and authenticity. Previous studies successfully used stable isotopes to separate organic and conventional products, but up to now, this approach was not tested for organic grassland hay and soil. Moreover, isotopic abundances could be a powerful tool to elucidate differences in ecosystem functioning and driving mechanisms of element cycling in organic and conventional management systems. Here, we studied the δ(15)N and δ(13)C isotopic composition of soil and hay samples of 21 organic and 34 conventional grasslands in two German regions. We also used Δδ(15)N (δ(15)N plant - δ(15)N soil) to characterize nitrogen dynamics. In order to detect temporal trends, isotopic abundances in organic grasslands were related to the time since certification. Furthermore, discriminant analysis was used to test whether the respective management type can be deduced from observed isotopic abundances. Isotopic analyses revealed no significant differences in δ(13)C in hay and δ(15)N in both soil and hay between management types, but showed that δ(13)C abundances were significantly lower in soil of organic compared to conventional grasslands. Δδ(15)N values implied that management types did not substantially differ in nitrogen cycling. Only δ(13)C in soil and hay showed significant negative relationships with the time since certification. Thus, our result suggest that organic grasslands suffered less from drought stress compared to conventional grasslands most likely due to a benefit of higher plant species richness, as previously shown by manipulative biodiversity experiments. Finally, it was possible to correctly classify about two third of the samples according to their management using isotopic abundances in soil and hay. However, as more than half of the organic samples were incorrectly classified, we infer that more research is needed to improve this approach before it can be efficiently

  4. Organic vs. Conventional Grassland Management: Do 15N and 13C Isotopic Signatures of Hay and Soil Samples Differ?

    PubMed Central

    Klaus, Valentin H.; Hölzel, Norbert; Prati, Daniel; Schmitt, Barbara; Schöning, Ingo; Schrumpf, Marion; Fischer, Markus; Kleinebecker, Till

    2013-01-01

    Distinguishing organic and conventional products is a major issue of food security and authenticity. Previous studies successfully used stable isotopes to separate organic and conventional products, but up to now, this approach was not tested for organic grassland hay and soil. Moreover, isotopic abundances could be a powerful tool to elucidate differences in ecosystem functioning and driving mechanisms of element cycling in organic and conventional management systems. Here, we studied the δ15N and δ13C isotopic composition of soil and hay samples of 21 organic and 34 conventional grasslands in two German regions. We also used Δδ15N (δ15N plant - δ15N soil) to characterize nitrogen dynamics. In order to detect temporal trends, isotopic abundances in organic grasslands were related to the time since certification. Furthermore, discriminant analysis was used to test whether the respective management type can be deduced from observed isotopic abundances. Isotopic analyses revealed no significant differences in δ13C in hay and δ15N in both soil and hay between management types, but showed that δ13C abundances were significantly lower in soil of organic compared to conventional grasslands. Δδ15N values implied that management types did not substantially differ in nitrogen cycling. Only δ13C in soil and hay showed significant negative relationships with the time since certification. Thus, our result suggest that organic grasslands suffered less from drought stress compared to conventional grasslands most likely due to a benefit of higher plant species richness, as previously shown by manipulative biodiversity experiments. Finally, it was possible to correctly classify about two third of the samples according to their management using isotopic abundances in soil and hay. However, as more than half of the organic samples were incorrectly classified, we infer that more research is needed to improve this approach before it can be efficiently used in practice

  5. 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.

  6. Analysis of the low molecular weight fraction of serum by LC-dual ESI-FT-ICR mass spectrometry: precision of retention time, mass, and ion abundance.

    PubMed

    Johnson, Kenneth L; Mason, Christopher J; Muddiman, David C; Eckel, Jeanette E

    2004-09-01

    This study quantifies the experimental uncertainty for LC retention time, mass measurement precision, and ion abundance obtained from replicate nLC-dual ESI-FT-ICR analyses of the low molecular weight fraction of serum. We used ultrafiltration to enrich the < 10-kDa fraction of components from the high-abundance proteins in a pooled serum sample derived from ovarian cancer patients. The THRASH algorithm for isotope cluster detection was applied to five replicate nLC-dual ESI-FT-ICR chromatograms. A simple two-level grouping algorithm was applied to the more than 7000 isotope clusters found in each replicate and identified 497 molecular species that appeared in at least four of the replicates. In addition, a representative set of 231 isotope clusters, corresponding to 188 unique molecular species, were manually interpreted to verify the automated algorithm and to set its tolerances. For nLC retention time reproducibility, 95% of the 497 species had a 95% confidence interval of the mean of +/- 0.9 min or less without the use of chromatographic alignment procedures. Furthermore, 95% of the 497 species had a mass measurement precision of < or = 3.2 and < or = 6.3 ppm for internally and externally calibrated spectra, respectively. Moreover, 95% of replicate ion abundance measurements, covering an ion abundance range of approximately 3 orders of magnitude, had a coefficient of variation of less than 62% without using any normalization functions. The variability of ion abundance was independent of LC retention time, mass, and ion abundance quartile. These measures of analytical reproducibility establish a statistical rationale for differentiating healthy and disease patient populations for the elucidation of biomarkers in the low molecular fraction of serum. Copyright 2004 American Chemical Society

  7. Barium isotope abundances in meteorites and their implications for early Solar System evolution

    NASA Astrophysics Data System (ADS)

    Bermingham, K. R.; Mezger, K.; Scherer, E. E.; Horan, M. F.; Carlson, R. W.; Upadhyay, D.; Magna, T.; Pack, A.

    2016-02-01

    Several nucleosynthetic processes contributed material to the Solar System, but the relative contributions of each process, the timing of their input into the solar nebula, and how well these components were homogenized in the solar nebula remain only partially constrained. The Ba isotope system is particularly useful in addressing these issues because Ba isotopes are synthesized via three nucleosynthetic processes (s-, r-, p-process). In this study, high precision Ba isotope analyses of 22 different whole rock chondrites and achondrites (carbonaceous chondrites, ordinary chondrites, enstatite chondrites, Martian meteorites, and eucrites) were performed to constrain the distribution of Ba isotopes on the regional scale in the Solar System. A melting method using aerodynamic levitation and CO2-laser heating was used to oxidize SiC, a primary carrier of Ba among presolar grains in carbonaceous chondrites. Destruction of these grains during the fusion process enabled the complete digestion of these samples. The Ba isotope data presented here are thus the first for which complete dissolution of the bulk meteorite samples was certain. Enstatite chondrites, ordinary chondrites, and all achondrites measured here possess Ba isotope compositions that are not resolved from the terrestrial composition. Barium isotope anomalies are evident in most of the carbonaceous chondrites analyzed, but the 135Ba anomalies are generally smaller than previously reported for similarly sized splits of CM2 meteorites. Variation in the size of the 135Ba anomaly is also apparent in fused samples from the same parent body (e.g., CM2 meteorites) and in different pieces from the same meteorite (e.g., Orgueil, CI). Here, we investigate the potential causes of variability in 135Ba, including the contribution of radiogenic 135Ba from the decay of 135Cs and incomplete homogenization of the presolar components on the <0.8 g sample scale.

  8. Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

    PubMed

    Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

    2008-01-01

    Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

  9. Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites.

    PubMed

    Becker, Harry; Walker, Richard J

    2003-09-11

    The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.

  10. ICT: isotope correction toolbox.

    PubMed

    Jungreuthmayer, Christian; Neubauer, Stefan; Mairinger, Teresa; Zanghellini, Jürgen; Hann, Stephan

    2016-01-01

    Isotope tracer experiments are an invaluable technique to analyze and study the metabolism of biological systems. However, isotope labeling experiments are often affected by naturally abundant isotopes especially in cases where mass spectrometric methods make use of derivatization. The correction of these additive interferences--in particular for complex isotopic systems--is numerically challenging and still an emerging field of research. When positional information is generated via collision-induced dissociation, even more complex calculations for isotopic interference correction are necessary. So far, no freely available tools can handle tandem mass spectrometry data. We present isotope correction toolbox, a program that corrects tandem mass isotopomer data from tandem mass spectrometry experiments. Isotope correction toolbox is written in the multi-platform programming language Perl and, therefore, can be used on all commonly available computer platforms. Source code and documentation can be freely obtained under the Artistic License or the GNU General Public License from: https://github.com/jungreuc/isotope_correction_toolbox/ {christian.jungreuthmayer@boku.ac.at,juergen.zanghellini@boku.ac.at} Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  11. Isotopic homogeneity of iron in the early solar nebula.

    PubMed

    Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

    2001-07-19

    The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

  12. Molecular Isotopic Distribution Analysis (MIDAs) with Adjustable Mass Accuracy

    NASA Astrophysics Data System (ADS)

    Alves, Gelio; Ogurtsov, Aleksey Y.; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  13. Molecular Isotopic Distribution Analysis (MIDAs) with adjustable mass accuracy.

    PubMed

    Alves, Gelio; Ogurtsov, Aleksey Y; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  14. Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

    NASA Astrophysics Data System (ADS)

    Muhammad, Syahidah; Frew, Russell; Hayman, Alan

    2015-02-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

  15. Compound-specific isotope analysis of diesel fuels in a forensic investigation

    PubMed Central

    Muhammad, Syahidah A.; Frew, Russell D.; Hayman, Alan R.

    2015-01-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples. PMID:25774366

  16. Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

    PubMed

    Leshin, L A; Mahaffy, P R; Webster, C R; Cabane, M; Coll, P; Conrad, P G; Archer, P D; Atreya, S K; Brunner, A E; Buch, A; Eigenbrode, J L; Flesch, G J; Franz, H B; Freissinet, C; Glavin, D P; McAdam, A C; Miller, K E; Ming, D W; Morris, R V; Navarro-González, R; Niles, P B; Owen, T; Pepin, R O; Squyres, S; Steele, A; Stern, J C; Summons, R E; Sumner, D Y; Sutter, B; Szopa, C; Teinturier, S; Trainer, M G; Wray, J J; Grotzinger, J P

    2013-09-27

    Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

  17. Generalists or Specialists: Stable Isotope Analysis of Humpback Whales (Megapteranoveangliae) to Infer Variation in Feeding Preferences

    NASA Astrophysics Data System (ADS)

    Brownstein, A.; Boswell, K. M.

    2016-02-01

    Though humpback whales (Megapteranovaeangliae) are commonly observed in coastal waters of the Gulf of Alaska, their massive size, behavior, and weather conditionsmake it difficult to make accurate observations regarding their feeding habits. These whales can be highly abundant during feeding aggregations, and given their large energetic needs, they have the potential to impact populations of ecologically important forage such as krill and herring. Previous studies in other areas, such as the Gulf of Maine and the North Pacific Ocean, classify humpback whales as generalists that can efficiently feed on both schooling fish and large zooplankton. In Prince William Sound, scientists have observed the humpbacks feedingprimarily on herring. It is unclear if these whalesfeed exclusively on fish prior to returning to the Sound, and can therefore be considered specialists. Stable isotope analysis of carbon and nitrogen were used to determine the preferred diet of humpback whales (N=22) in 6 sampling regions along the Gulf of Alaska. Isotope analyses were conducted on humpback whale skin, as well as local forage species and basal resources to be used in Bayesian isotope mixing models to elucidate the trophic relationships between whales and their prey, and provide insight to whether location is an important driver in prey selection. This information will not only lead to a better understanding of the potential to use tissue isotopes to elucidate foraging behaviors of humpback whales, but also offer insight into individual feeding preferences and how increasing whale populations may affect the populations of local forage in the future.

  18. Isotope ratio mass spectrometry in nutrition research

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

    Luke, A.H.

    Many of the biochemical pathways and processes that form the foundation of modern nutrition research was elucidated using stable isotopes as physiological tracers. Since the discovery of stable isotopes, improvements and innovations in mass spectrometry and chromatography have led to greatly expanded applications. This research project was designed to evaluate gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as a tool for isotopic tracer studies and to delineate the operational parameters for the analysis of {sup 13}C-labeled cholesterol, leucine and {alpha}-ketoisocaproate. The same isotope ratio mass spectrometer was then used as the base instrument for the ratio mass spectrometer was then usedmore » as the base instrument for the development of two additional inlet systems: a continuous-flow inlet for the analyses of {sup 13}C and {sup 18}O as CO{sub 2} and a filament inlet for on-line combustion and isotopic analysis of non-volatile organic compounds. Each of these three inlets was evaluated and their utility in nutrition research illustrated. GC/C/IRMS was used to analyze cholesterol, leucine and {alpha}-ketoisocaproate with good accuracy, precision and little isotopic memory. For all three compounds the detection limits achieved well surpassed currently used technologies. For compounds that can be well separated by GC, GC/C/IRMS is a valuable analytical tool. The continuous-flow inlet provided good accuracy and precision for measurements of {sup 13}CO{sub 2} from breath tests and {sup 18}O as CO{sub 2} from total energy expenditure tests. Most importantly, the continuous-flow inlet increased sample throughput by at least a factor of three over conventional analytical techniques. The filament inlet provided accurate and precise {sup 13}C ratio measurements of both natural abundance and enriched standards of non-volatile organic compounds of physiological interest.« less

  19. Compound-Specific Chlorine Isotope Analysis of Tetrachloromethane and Trichloromethane by Gas Chromatography-Isotope Ratio Mass Spectrometry vs Gas Chromatography-Quadrupole Mass Spectrometry: Method Development and Evaluation of Precision and Trueness.

    PubMed

    Heckel, Benjamin; Rodríguez-Fernández, Diana; Torrentó, Clara; Meyer, Armin; Palau, Jordi; Domènech, Cristina; Rosell, Mònica; Soler, Albert; Hunkeler, Daniel; Elsner, Martin

    2017-03-21

    Compound-specific chlorine isotope analysis of tetrachloromethane (CCl 4 ) and trichloromethane (CHCl 3 ) was explored by both, gas chromatography-isotope ratio mass spectrometry (GC-IRMS) and GC-quadrupole MS (GC-qMS), where GC-qMS was validated in an interlaboratory comparison between Munich and Neuchâtel with the same type of commercial GC-qMS instrument. GC-IRMS measurements analyzed CCl isotopologue ions, whereas GC-qMS analyzed the isotopologue ions CCl 3 , CCl 2 , CCl (of CCl 4 ) and CHCl 3 , CHCl 2 , CHCl (of CHCl 3 ), respectively. Lowest amount dependence (good linearity) was obtained (i) in H-containing fragment ions where interference of 35 Cl- to 37 Cl-containing ions was avoided; (ii) with tuning parameters favoring one predominant rather than multiple fragment ions in the mass spectra. Optimized GC-qMS parameters (dwell time 70 ms, 2 most abundant ions) resulted in standard deviations of 0.2‰ (CHCl 3 ) and 0.4‰ (CCl 4 ), which are only about twice as large as 0.1‰ and 0.2‰ for GC-IRMS. To compare also the trueness of both methods and laboratories, samples from CCl 4 and CHCl 3 degradation experiments were analyzed and calibrated against isotopically different reference standards for both CCl 4 and CHCl 3 (two of each). Excellent agreement confirms that true results can be obtained by both methods provided that a consistent set of isotopically characterized reference materials is used.

  20. Use of stable isotope analysis in determining aquatic food webs

    EPA Science Inventory

    Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

  1. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

    Harilal, Sivanandan S.; Brumfield, Brian E.; LaHaye, Nicole L.

    2018-04-20

    This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

  2. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

    DOE PAGES

    Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

    2018-04-20

    This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

  3. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

    Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

    This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

  4. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

    DOE PAGES

    Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

    2018-06-01

    This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

  5. Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

    Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

    This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

  6. Stable isotope analysis at the molecular level: A new approach for determining the origins of amino acids in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta C-13 values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in C-13 relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta C-13 values (+5 to +30 per mill, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary resutls are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.

  7. Chlorine Isotope Ratios in M Giants and S Stars

    NASA Astrophysics Data System (ADS)

    Maas, Zachary; Pilachowski, C. A.

    2018-01-01

    Chlorine is an odd-Z, light element that has been poorly studied in stars. Recently, the first stellar abundance measurements of the isotopologue 35Cl were made and the 35Cl/37Cl ratio was derived in RZ Ari (Maas et al. 2016). Additional abundance measurements are necessary to understand the Galactic chemical evolution and complex nucleosynthesis of Cl. The Cl isotope ratio in particular is important in distinguishing contributions from different nucleosynthesis sites to the surface abundances of stars. For example, current nucloesynthesis models predict that both isotopes of Cl are produced primarily during core collapse supernovae (CCSNe) with the energy and progenitor mass impacting the isotopic ratio of the ejected material. In addition to CCSNe, 37Cl is formed by the s-process both in massive stars and in AGB stars, and 35Cl may be produced from neutrino spallation. Understanding the formation of the Cl isotopes is also important to studies of the interstellar medium (ISM). A range of Cl isotope ratios mainly between 2 - 3.5 have been measured in star forming regions, in the circumstellar envelopes of evolved stars, and in proto-stellar cores using Cl bearing molecules. Additional measurements of the Cl isotope ratio in nearby stars will test nucleosynthesis models and allow comparisons with the range of isotope ratios observed in the ISM.We build on the results of Maas et al. (2016) by measuring the Cl isotope ratio in six M giants and four S stars using R~50,000 resolution spectra from Phoenix on Gemini South. We find no significant difference between the average Cl isotope ratios in the M stars and S stars and our measurements are consistent with the range of values seen in the ISM. We also find the average Cl ratio to be larger than the predicted isotope ratio of 1.8 for the solar neighborhood. Finally, two S stars, GG Pup and WY Pyx, show anomalously strong HCl features with equivalent widths ~3-5 times larger than the HCl features of other stars of

  8. Elemental, isotopic and molecular abundances in comets

    NASA Technical Reports Server (NTRS)

    Delsemme, A. H.

    1986-01-01

    The chemical composition of comet nuclei and the factors affecting it are discussed, summarizing the results of recent theoretical, experimental, and observational investigations. Consideration is given to the evidence supporting the view that the nucleus is radially differentiation (except for a thin outer layer), surface differentiation by heat processing and outgassing, and mantle buildup on an undifferentiated core. The nature of the refractory and volatile components is examined, and the elemental and isotopic compositions are given in tables and characterized. The uncertain (except for H2O) molecular composition of the volatile fraction is considered, and it is suggested that some oxides or aldehydes (such as CO, CO2, and H2CO), but no large amounts of fully hydrogenated compounds (such as CH4 and NH3) are included.

  9. Rare-earth abundances in chondritic meteorites

    NASA Technical Reports Server (NTRS)

    Evensen, N. M.; Hamilton, P. J.; Onions, R. K.

    1978-01-01

    Fifteen chondrites, including eight carbonaceous chondrites, were analyzed for rare earth element abundances by isotope dilution. Examination of REE for a large number of individual chondrites shows that only a small proportion of the analyses have flat unfractionated REE patterns within experimental error. While some of the remaining analyses are consistent with magmatic fractionation, many patterns, in particular those with positive Ce anomalies, can not be explained by known magmatic processes. Elemental abundance anomalies are found in all major chondrite classes. The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibrium or were introduced at a late stage of chondrite formation. Large-scale segregation of gas and condensate is implied, and bulk variations in REE abundances between planetary bodies is possible.

  10. Light Nuclei and Isotope Abundances in Cosmic Rays. Results from AMS-01

    NASA Astrophysics Data System (ADS)

    Tomassetti, N.

    2011-06-01

    Observations of the chemical and isotopic composition of light cosmic-ray nuclei can be used to constrain the propagation models. Nearly 200,000 light nuclei (Z > 2) have been observed by AMS-01 during the 10-day flight STS-91 in June 1998. Using these data, we have measured Li, Be, B and C in the kinetic energy range 0.35 - 45 GeV/nucleon. In this proceeding, our charge and isotopic composition results are presented and discussed.

  11. MYCORRHIZAL VS. SAPROTROPHIC STATUS OF FUNGI: THE ISOTOPIC EVIDENCE

    EPA Science Inventory

    Relative abundance of carbon (C) and nitrogen (N) isotopes in fungal sporocarps may prove useful in unraveling fungal roles in ecosystems. Sporocarps of known mycorrhizal or saprotrophic genera were collected from a single site in Oregon and isotopically compared to foliage, litt...

  12. Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

    USGS Publications Warehouse

    Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

    2015-01-01

    Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN

  13. Water Table Depth Reconstruction in Ombrotrophic Peatlands Using Biomarker Abundance Ratios and Compound-Specific Hydrogen Isotope Composition

    NASA Astrophysics Data System (ADS)

    Nichols, J. E.; Jackson, S. T.; Booth, R. K.; Pendall, E. G.; Huang, Y.

    2005-12-01

    Sediment cores from ombrotrophic peat bogs provide sensitive records of changes in precipitation/evaporation (P/E) balance. Various proxies have been developed to reconstruct surface moisture conditions in peat bogs, including testate amoebae, plant macrofossils, and peat humification. Studying species composition of testate amoeba assemblages is time consuming and requires specialized training. Humification index can be influenced by environmental factors other than moisture balance. The plant macrofossil proxy is less quantitative and cannot be performed on highly decomposed samples. We demonstrate that the ratio of C23 alkane to C29 alkane abundance may provide a simple alternative or complementary means of tracking peatland water-table depth. Data for this proxy can be collected quickly using a small sample (100 mg dry). Water-table depth decreases during drought, and abundance of Sphagnum, the dominant peat-forming genus, decreases as vascular plants increase. Sphagnum moss produces mainly medium chain-length alkanes (C21-C25) while vascular plants (grasses and shrubs) produce primarily longer chain-length alkanes (C27-C31). Therefore, C23:C29 n-alkane ratios quantitatively track the water table depth fluctuations in peat bogs. We compared C23:C29 n-alkane ratios in a core from Minden Bog (southeastern Michigan) with water table depth reconstructions based on testate-amoeba assemblages and humification. The 184-cm core spans the past ~3kyr of continuous peat deposition in the bog. Our results indicate that the alkane ratios closely track the water table depth variations, with C29 most abundant during droughts. We also explored the use of D/H ratios in Sphagnum biomarkers as a water-table depth proxy. Compound-specific hydrogen isotope ratio analyses were performed on Sphagnum biomarkers: C23 and C25 alkane and C24 acid. Dry periods are represented in these records by an enrichment of deuterium in these Sphagnum-specific compounds. These events also correlate

  14. Lipid Extraction Techniques for Stable Isotope Analysis and Ecological Assays.

    PubMed

    Elliott, Kyle H; Roth, James D; Crook, Kevin

    2017-01-01

    Lipid extraction is an important component of many ecological and ecotoxicological measurements. For instance, percent lipid is often used as a measure of body condition, under the assumption that those individuals with higher lipid reserves are healthier. Likewise, lipids are depleted in 13 C compared with protein, and it is consequently a routine to remove lipids prior to measuring carbon isotopes in ecological studies so that variation in lipid content does not obscure variation in diet. We provide detailed methods for two different protocols for lipid extraction: Soxhlet apparatus and manual distillation. We also provide methods for polar and nonpolar solvents. Neutral (nonpolar) solvents remove some lipids but few non-lipid compounds, whereas polar solvents remove most lipids but also many non-lipid compounds. We discuss each of the methods and provide guidelines for best practices. We recommend that, for stable isotope analysis, researchers test for a relationship between the change in carbon stable isotope ratio and the amount of lipid extracted to see if the degree of extraction has an impact on isotope ratios. Stable isotope analysis is widely used by ecologists, and we provide a detailed methodology that minimizes known biases.

  15. The Stanford-U.S. Geological Survey SHRIMP ion microprobe--a tool for micro-scale chemical and isotopic analysis

    USGS Publications Warehouse

    Bacon, Charles R.; Grove, Marty; Vazquez, Jorge A.; Coble, Matthew A.

    2012-01-01

    Answers to many questions in Earth science require chemical analysis of minute volumes of minerals, volcanic glass, or biological materials. Secondary Ion Mass Spectrometry (SIMS) is an extremely sensitive analytical method in which a 5–30 micrometer diameter "primary" beam of charged particles (ions) is focused on a region of a solid specimen to sputter secondary ions from 1–5 nanograms of the sample under high vacuum. The elemental abundances and isotopic ratios of these secondary ions are determined with a mass spectrometer. These results can be used for geochronology to determine the age of a region within a crystal thousands to billions of years old or to precisely measure trace abundances of chemical elements at concentrations as low as parts per billion. A partnership of the U.S. Geological Survey and the Stanford University School of Earth Sciences operates a large SIMS instrument, the Sensitive High-Resolution Ion Microprobe with Reverse Geometry (SHRIMP–RG) on the Stanford campus.

  16. SHRIMP-SI Multiple Sulfur Isotope Analysis of Sulfides from Brazilian Deposits: Analytical Capability to Resolve Single Grain Textural Complexities and Distinct Sulfur Sources

    NASA Astrophysics Data System (ADS)

    Ireland, T. R.; Teles, G. D. S.; Chemale, F., Jr.; Avila, J.

    2016-12-01

    The Archean atmosphere is thought to be several times more reducing than the present day atmosphere, and the occurrence of Mass Independent Fractionation of Sulfur isotopes (MIF-S) in sulfides of sedimentary and volcanogenic rocks older than 2.45 Ga reinforces it. The most accepted mechanism to generate MIF-S requires photochemical reactions with volcanogenic SO2 in an anoxic atmosphere (O2 levels <10-5 PAL). The identification of MIF-S, noted as Δ33S and Δ36S, requires precise measurements of less abundant 33S and 36S isotopes, which were first attained by bulk isotope analyses. However, in-situ analysis has become essential, as many of ancient sulfide samples have suffered post-depositional processes, and their primary isotopic signature from the atmosphere are now overprinted by mass-dependent fractionation processes. High-precision and resolution in situ measurements of 32S, 33S, 34S and 36S in sulfides can be achieved by SHRIMP-SI, which allows isotopic determinations with internal errors better than 0.05‰ for Δ33S and 0.2‰ for Δ36S (2SE), and reproducibility about 0.1‰ for Δ33S and better than 0.5‰ for Δ36S (2SD). Examples of the SHRIMP-SI capability are provided by multiple sulfur isotope analysis of samples from Brazil, the Au-(U) and pyrite deposits of Jacobina Basin and the massive sulfide deposits of the 3.3 Ga Mundo Novo Greenstone Belt. The level of precision and spatial resolution achievable with SHRIMP-SI allowed the isotopic distinction between sedimentary and post-depositional pyrites in Jacobina Basin, as well as the identification of different sulfur sources in the Mundo Novo Greenstone Belt VMS deposits.

  17. Monitoring Microbial Mineralization Using Reverse Stable Isotope Labeling Analysis by Mid-Infrared Laser Spectroscopy

    PubMed Central

    2017-01-01

    Assessing the biodegradation of organic compounds is a frequent question in environmental science. Here, we present a sensitive, inexpensive, and simple approach to monitor microbial mineralization using reverse stable isotope labeling analysis (RIL) of dissolved inorganic carbon (DIC). The medium for the biodegradation assay contains regular organic compounds and 13C-labeled DIC with 13C atom fractions (x(13C)DIC) higher than natural abundance (typically 2–50%). The produced CO2 (x(13C) ≈ 1.11%) gradually dilutes the initial x(13C)DIC allowing to quantify microbial mineralization using mass-balance calculations. For 13C-enriched CO2 samples, a newly developed isotope ratio mid-infrared spectrometer was introduced with a precision of x(13C) < 0.006%. As an example for extremely difficult and slowly degradable compounds, CO2 production was close to the theoretical stoichiometry for anaerobic naphthalene degradation by a sulfate-reducing enrichment culture. Furthermore, we could measure the aerobic degradation of dissolved organic carbon (DOC) adsorbed to granular activated carbon in a drinking water production plant, which cannot be labeled with 13C. Thus, the RIL approach can be applied to sensitively monitor biodegradation of various organic compounds under anoxic or oxic conditions. PMID:28903553

  18. 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...

  19. Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Herbst, Eric; Adams, Nigel G.; Smith, David; Defrees, D. J.

    1987-01-01

    Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2(+) (HD)=C2HD(+)(H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.0l-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.

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

    PubMed

    Preston, Tom

    2014-01-01

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

  1. Isotope ratio analysis by Orbitrap mass spectrometry

    NASA Astrophysics Data System (ADS)

    Eiler, J. M.; Chimiak, L. M.; Dallas, B.; Griep-Raming, J.; Juchelka, D.; Makarov, A.; Schwieters, J. B.

    2016-12-01

    Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but various limitations in sample size and type or (for IRMS) resolution have so far prevented the creation of a truly general technique. We will discuss the initial findings of a technique based on Fourier transform mass spectrometry, using the Thermo Scientific Q Exactive GC — an instrument that contains an Orbitrap mass analyzer. Fourier transform mass spectrometry is marked by exceptionally high mass resolutions (the Orbitrap reaches M/ΔM in the range 250,000-1M in the mass range of greatest interest, 50-200 amu). This allows for resolution of a large range of nearly isobaric interferences for isotopologues of volatile and semi-volatile compounds (i.e., involving isotopes of H, C, N, O and S). It also provides potential to solve very challenging mass resolution problems for isotopic analysis of other, heavier elements. Both internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap typically conform to shot-noise limits down to levels of 0.2 ‰ (1SE), and routinely in the range 0.5-1.0 ‰, with similar accuracy when standardized to concurrently run reference materials. Such measurements can be made without modifications to the ion optics of the Q Exactive GC, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive GC permits analysis of sub-nanomolar samples and quantification of multiply-substituted species. The site-specific capability of this instrument arises from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites. We will present applications of this technique to the biological and abiological chemistry of amino acids, forensic identification of hydrocarbon

  2. Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Cook, Jamie; Elsila, Jamie E.; Stern J. C.; Glavin, D. P.; Dworkin, J. P.

    2008-01-01

    Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

  3. Electrochemically controlled iron isotope fractionation

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; Young, Edward D.; Kavner, Abby

    2010-02-01

    Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

  4. Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

    USGS Publications Warehouse

    Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

    2009-01-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

  5. Chemical abundance analysis of 13 southern symbiotic giants from high-resolution spectra at ˜1.56 μm

    NASA Astrophysics Data System (ADS)

    Gałan, Cezary; Mikołajewska, Joanna; Hinkle, Kenneth H.; Joyce, Richard R.

    2017-04-01

    Symbiotic stars (SySt) are binaries composed of a star in the later stages of evolution and a stellar remnant. The enhanced mass-loss from the giant drives interacting mass exchange and makes these systems laboratories for understanding binary evolution. Studies of the chemical compositions are particularly useful since this parameter has strong impact on the evolutionary path. The previous paper in this series presented photospheric abundances for 24 giants in S-type SySt enabling a first statistical analysis. Here, we present results for an additional sample of 13 giants. The aims are to improve statistics of chemical composition involved in the evolution of SySt, to study evolutionary status, mass transfer and to interpret this in terms of Galactic populations. High-resolution, near-IR spectra are used, employing the spectrum synthesis method in a classical approach, to obtain abundances of CNO and elements around the iron peak (Fe, Ti, Ni). Low-resolution spectra in the region around the Ca II triplet were used for spectral classification. The metallicities obtained cover a wide range with a maximum around ˜- 0.2 dex. The enrichment in the 14N isotope indicates that these giants have experienced the first dredge-up. Relative O and Fe abundances indicate that most SySt belong to the Galactic disc; however, in a few cases, the extended thick-disc/halo is suggested. Difficult to explain, relatively high Ti abundances can indicate that adopted microturbulent velocities were too small by ˜0.2-0.3 km s-1. The revised spectral types for V2905 Sgr, and WRAY 17-89 are M3 and M6.5, respectively.

  6. Abundance Analysis of the Helium Weak Star 20-TAURI

    NASA Astrophysics Data System (ADS)

    Mon, M.; Hirata, R.; Sadakane, K.

    An abundance analysis of the helium-weak star 20 Tauri is performed with a fully line-blanketed model atmosphere. The adopted atmospheric parameters are Teff =12600 K and log g=3.2. These values are lower by about 1000 K in Teff and 0.3 in log g than those used in previous investigations, and 20 Tau is the coolest star among the group of helium-weak star. A value of log N(He)/N(H)=-1.7 is found from the average of six He I lines. Mg, Si, Ca, and Ni are underabundant, while P and Mn are overabundant. The abundances of C, Ti, Cr, and Fe coincide with the solar values within ±0.3 dex. Upper limits of the abundances of S, Sc, and Sr are estimated and these elements are not overabundant. The observed abundance pattern in 20 Tau is quite different from those in other helium-weak stars, while it shows a mild characteristic of Mn-Hg stars.

  7. Isotopic And Geochemical Investigations Of Meteorites

    NASA Technical Reports Server (NTRS)

    Walker, Richard J.

    2005-01-01

    The primary goals of our research over the past four years are to constrain the timing of certain early planetary accretion/differentiation events, and to constrain the proportions and provenance of materials involved in these processes. This work was achieved via the analysis and interpretation of long- and short-lived isotope systems, and the study of certain trace elements. Our research targeted these goals primarily via the application of the Re-187, Os-187, Pt-190 Os-186 Tc-98 Ru-99 and Tc-99 Ru-99 isotopic systems, and the determination/modeling of abundances of the highly siderophile elements (HSE; including Re, Os, Ir, Ru, Pd, Pt, and maybe Tc). The specific events we examined include the segregation and crystallization histories of asteroidal cores, the accretion and metamorphic histories of chondrites and chondrite components, and the accretionary and differentiation histories of Mars and the Moon.

  8. 3He Abundances in Planetary Nebulae

    NASA Astrophysics Data System (ADS)

    Guzman-Ramirez, Lizette

    2017-10-01

    Determination of the 3He isotope is important to many fields of astrophysics, including stellar evolution, chemical evolution, and cosmology. The isotope is produced in stars which evolve through the planetary nebula phase. Planetary nebulae are the final evolutionary phase of low- and intermediate-mass stars, where the extensive mass lost by the star on the asymptotic giant branch is ionised by the emerging white dwarf. This ejecta quickly disperses and merges with the surrounding ISM. 3He abundances in planetary nebulae have been derived from the hyperfine transition of the ionised 3He, 3He+, at the radio rest frequency 8.665 GHz. 3He abundances in PNe can help test models of the chemical evolution of the Galaxy. Many hours have been put into trying to detect this line, using telescopes like the Effelsberg 100m dish of the Max Planck Institute for Radio Astronomy, the National Radio Astronomy Observatory (NRAO) 140-foot telescope, the NRAO Very Large Array, the Arecibo antenna, the Green Bank Telescope, and only just recently, the Deep Space Station 63 antenna from the Madrid Deep Space Communications Complex.

  9. Chemical Abundance Analysis of Moving Group W11450 (Latham 1)

    NASA Astrophysics Data System (ADS)

    O'Connell, Julia E.; Martens, Kylee; Frinchaboy, Peter M.

    2016-12-01

    We present elemental abundances for all seven stars in Moving Group W11450 (Latham 1) to determine if they may be chemically related. These stars appear to be both spatially and kinematically related, but no spectroscopic abundance analysis exists in literature. Abundances for eight elements were derived via equivalent width analyses of high-resolution (R ˜ 60,000), high-signal-to-noise ratio (< {{S}}/{{N}}> ˜ 100) spectra obtained with the Otto Struve 2.1 m telescope and the Sandiford Echelle Spectrograph at McDonald Observatory. The large star-to-star scatter in metallicity, -0.55 ≤ [Fe/H] ≤slant 0.06 dex (σ = 0.25), implies these stars were not produced from the same chemically homogeneous molecular cloud, and are therefore not part of a remnant or open cluster as previously proposed. Prior to this analysis, it was suggested that two stars in the group, W11449 and W11450, are possible wide binaries. The candidate wide binary pair show similar chemical abundance patterns with not only iron but with other elements analyzed in this study, suggesting the proposed connection between these two stars may be real.

  10. Volatile abundances and oxygen isotopes in basaltic to dacitic lavas on mid-ocean ridges: The role of assimilation at spreading centers

    USGS Publications Warehouse

    Wanless, V.D.; Perfit, M.R.; Ridley, W.I.; Wallace, P.J.; Grimes, Craig B.; Klein, E.M.

    2011-01-01

    Most geochemical variability in MOR basalts is consistent with low- to moderate-pressure fractional crystallization of various mantle-derived parental melts. However, our geochemical data from MOR high-silica glasses, including new volatile and oxygen isotope data, suggest that assimilation of altered crustal material plays a significant role in the petrogenesis of dacites and may be important in the formation of basaltic lavas at MOR in general. MOR high-silica andesites and dacites from diverse areas show remarkably similar major element trends, incompatible trace element enrichments, and isotopic signatures suggesting similar processes control their chemistry. In particular, very high Cl and elevated H2O concentrations and relatively light oxygen isotope ratios (~ 5.8‰ vs. expected values of ~ 6.8‰) in fresh dacite glasses can be explained by contamination of magmas from a component of ocean crust altered by hydrothermal fluids. Crystallization of silicate phases and Fe-oxides causes an increase in δ18O in residual magma, but assimilation of material initially altered at high temperatures results in lower δ18O values. The observed geochemical signatures can be explained by extreme fractional crystallization of a MOR basalt parent combined with partial melting and assimilation (AFC) of amphibole-bearing altered oceanic crust. The MOR dacitic lavas do not appear to be simply the extrusive equivalent of oceanic plagiogranites. The combination of partial melting and assimilation produces a distinct geochemical signature that includes higher incompatible trace element abundances and distinct trace element ratios relative to those observed in plagiogranites.

  11. Stable isotopic analysis of human diet in the Marianas Archipelago, western Pacific.

    PubMed

    Ambrose, S H; Butler, B M; Hanson, D B; Hunter-Anderson, R L; Krueger, H W

    1997-11-01

    Proportions of marine vs. terrestrial resources in prehistoric human diets in the southern Mariana Islands (Guam, Rota, Saipan), Micronesia, have been estimated by analysis of stable isotope ratios of carbon and nitrogen in bone collagen and of carbon in apatite. The isotopic composition of marine and terrestrial food resources from the Marianas have also been determined. Experimental evidence shows that collagen carbon isotopes mainly reflect those of dietary protein sources and thus overestimate the contribution of marine animal foods. Marine protein consumption apparently ranges from approximately 20% to approximately 50% on these islands. Experiments also demonstrate the carbon isotope ratio of bone apatite carbonate accurately reflects that of the whole diet. Carbonate carbon isotope data suggest some individuals consumed significant amounts of 13C-enriched (C4) plants or seaweeds. Sugar cane is an indigenous C4 crop and seaweeds are eaten throughout the Pacific, but they have not been considered by archaeologists to have been prehistoric dietary staples. Apatite carbon isotope analysis has apparently identified previously unrecognized prehistoric dietary adaptations in the Mariana Islands, but this must be confirmed by archaeobotanical evidence.

  12. DANCEing with the Stars: Measuring Neutron Capture on Unstable Isotopes with DANCE

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

    Couture, A.; Bond, E.; Bredeweg, T. A.

    2009-03-10

    Isotopes heavier than iron are known to be produced in stars through neutron capture processes. Two major processes, the slow (s) and rapid (r) processes are each responsible for 50% of the abundances of the heavy isotopes. The neutron capture cross sections of the isotopes on the s process path reveal information about the expected abundances of the elements as well as stellar conditions and dynamics. Until recently, measurements on unstable isotopes, which are most important for determining stellar temperatures and reaction flow, have not been experimentally feasible. The Detector for Advance Neutron Capture Experiments (DANCE) located at the Losmore » Alamos Neutron Science Center (LANSCE) was designed to perform time-of-flight neutron capture measurements on unstable isotopes for nuclear astrophysics, stockpile stewardship, and reactor development. DANCE is a 4-{pi}BaF{sub 2} scintillator array which can perform measurements on sub-milligram samples of isotopes with half-lives as short as a few hundred days. These cross sections are critical for advancing our understanding of the production of the heavy isotopes.« less

  13. Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

    NASA Astrophysics Data System (ADS)

    Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

    2013-04-01

    Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

  14. Stable isotope analysis of Pacific salmon: insight into trophic status and oceanographic conditions over the last 30 years

    NASA Astrophysics Data System (ADS)

    Satterfield, Franklin R.; Finney, Bruce P.

    Food web interactions and the response of Pacific salmon to physical processes in the North Pacific Ocean over interannual and interdecadal timescales are explored using naturally occurring stable isotope ratios of carbon ( 13C/ 12C) and nitrogen ( 15N/ 14N). Stable isotope analyses of five species of sexually mature North Pacific salmon from Alaska ( Oncorhynchus spp.) cluster into three groups: chinook salmon ( O. tshawytscha) have the highest values, followed by coho ( O. kisutch), with chum ( O. keta), sockeye ( O. nerka), and pink ( O. gorbuscha) together having the lowest values. Although detailed isotopic data on salmon prey are lacking, there are limited data on relevant prey items from areas in which they are found in high abundance. These data suggest that the characteristics of the sockeye, pink and chum we have analyzed are compatible with their diets including open ocean squid and zooplankton, which are in general agreement with stomach content analyses. Isotope relationships between muscle and scale show consistent relationships for both δ13C ( R2=0.98) and δ 15N ( R2=0.90). Thus, scales, which have been routinely archived for many systems, can be used for retrospective analyses. Archived sockeye salmon scales spanning 1966-1999 from Red Lake, Kodiak Island, Alaska were analyzed for their stable isotope ratios of carbon and nitrogen. The δ15N record displays a decreasing trend of ~3‰ from 1969-1982 and an increasing trend of ~3‰ from 1982-1992, while the variations in δ13C are relatively minor. These trends may result from factors such as shifts in trophic level of feeding and/or feeding location, or may originate at the base of the food web via changes in processes such as nutrient cycling or primary productivity. Detailed studies on prey isotopic variability and its controls are needed to distinguish between these factors, and thus to improve the use of stable isotope analysis as a tool to learn more about present and past ecosystem change

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

    PubMed

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

    2011-03-01

    Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

  16. The isotopic composition of cosmic-ray calcium

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.; George, J. S.; Binns, W. R.; Christian, E. R.; Cummings, A. C.; Davis, A. J.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A.; Stone, E. C.; hide

    2001-01-01

    We find that the relative abundance of cosmic ray calcium isotopes in the cosmic-ray source are very similar to those found in solar-system material, in spite of the fact that different types of stars are thought to be responsible for producing these two isotopes. This observation is consistent with the view that cosmic rays are derived from a mixed sample of interstellar matter.

  17. Analysis of hydrogen isotope mixtures

    DOEpatents

    Villa-Aleman, Eliel

    1994-01-01

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

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

    PubMed

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

    2009-11-01

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

  19. s-Processing from MHD-induced mixing and isotopic abundances in presolar SiC grains

    NASA Astrophysics Data System (ADS)

    Palmerini, S.; Trippella, O.; Busso, M.; Vescovi, D.; Petrelli, M.; Zucchini, A.; Frondini, F.

    2018-01-01

    In the past years the observational evidence that s-process elements from Sr to Pb are produced by stars ascending the so-called Asymptotic Giant Branch (or "AGB") could not be explained by self-consistent models, forcing researchers to extensive parameterizations. The crucial point is to understand how protons can be injected from the envelope into the He-rich layers, yielding the formation of 13C and then the activation of the 13C (α,n)16O reaction. Only recently, attempts to solve this problem started to consider quantitatively physically-based mixing mechanisms. Among them, MHD processes in the plasma were suggested to yield mass transport through magnetic buoyancy. In this framework, we compare results of nucleosynthesis models for Low Mass AGB Stars (M≲ 3M⊙), developed from the MHD scenario, with the record of isotopic abundance ratios of s-elements in presolar SiC grains, which were shown to offer precise constraints on the 13C reservoir. We find that n-captures driven by magnetically-induced mixing can indeed account for the SiC data quite well and that this is due to the fact that our 13C distribution fulfils the above constraints rather accurately. We suggest that similar tests should be now performed using different physical models for mixing. Such comparisons would indeed improve decisively our understanding of the formation of the neutron source.

  20. Rare earth element abundances in presolar SiC

    NASA Astrophysics Data System (ADS)

    Ireland, T. R.; Ávila, J. N.; Lugaro, M.; Cristallo, S.; Holden, P.; Lanc, P.; Nittler, L.; Alexander, C. M. O'D.; Gyngard, F.; Amari, S.

    2018-01-01

    Individual isotope abundances of Ba, lanthanides of the rare earth element (REE) group, and Hf have been determined in bulk samples of fine-grained silicon carbide (SiC) from the Murchison CM2 chondrite. The analytical protocol involved secondary ion mass spectrometry with combined high mass resolution and energy filtering to exclude REE oxide isobars and Si-C-O clusters from the peaks of interest. Relative sensitivity factors were determined through analysis of NIST SRM reference glasses (610 and 612) as well as a trace-element enriched SiC ceramic. When normalised to chondrite abundances, the presolar SiC REE pattern shows significant deficits at Eu and Yb, which are the most volatile of the REE. The pattern is very similar to that observed for Group III refractory inclusions. The SiC abundances were also normalised to s-process model predictions for the envelope compositions of low-mass (1.5-3 M⊙) AGB stars with close-to-solar metallicities (Z = 0.014 and 0.02). The overall trace element abundances (excluding Eu and Yb) appear consistent with the predicted s-process patterns. The depletions of Eu and Yb suggest that these elements remained in the gas phase during the condensation of SiC. The lack of depletion in some other moderately refractory elements (like Ba), and the presence of volatile elements (e.g. Xe) indicates that these elements were incorporated into SiC by other mechanisms, most likely ion implantation.

  1. Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George

    2004-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

  2. The lack of potassium-isotopic fractionation in Bishunpur chondrules

    USGS Publications Warehouse

    Alexander, C.M. O'D.; Grossman, J.N.; Wang, Jingyuan; Zanda, B.; Bourot-Denise, M.; Hewins, R.H.

    2000-01-01

    In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K-isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ41K compositions that were normal within error (typically ±3%, 2s̀). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large 41K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ41K is produced by ∼12% loss of K. The range of L-chondrite-normalized K/Al ratios (a measure of the K-elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L-chondrite-like K abundances and the K loss occurred via Rayleigh fractionation, the most K-depleted chondrules would have had compositions of up to δ41K ≅ 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K-isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K-isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim-matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have

  3. Multivariate Stable Isotope Analysis to Determine Linkages between Benzocaine Seizures

    NASA Astrophysics Data System (ADS)

    Kemp, H. F.; Meier-Augenstein, W.; Collins, M.; Salouros, H.; Cunningham, A.; Harrison, M.

    2012-04-01

    In July 2010, a woman was jailed for nine years in the UK after the prosecution successfully argued that attempting to import a cutting agent was proof of involvement in a conspiracy to supply Cocaine. That landmark ruling provided law enforcement agencies with much greater scope to tackle those involved in this aspect of the drug trade, specifically targeting those importing the likes of benzocaine or lidocaine. Huge quantities of these compounds are imported into the UK and between May and August 2010, four shipments of Benzocaine amounting to more then 4 tons had been seized as part of Operation Kitley, a joint initiative between the UK Border Agency and the Serious Organised Crime Agency (SOCA). By diluting cocaine, traffickers can make it go a lot further for very little cost, leading to huge profits. In recent years, dealers have moved away from inert substances, like sugar and baby milk powder, in favour of active pharmaceutical ingredients (APIs), including anaesthetics like Benzocaine and Lidocaine. Both these mimic the numbing effect of cocaine, and resemble it closely in colour, texture and some chemical behaviours, making it easier to conceal the fact that the drug has been diluted. API cutting agents have helped traffickers to maintain steady supplies in the face of successful interdiction and even expand the market in the UK, particularly to young people aged from their mid teens to early twenties. From importation to street-level, the purity of the drug can be reduced up to a factor of 80 and street level cocaine can have a cocaine content as low as 1%. In view of the increasing use of Benzocaine as cutting agent for Cocaine, a study was carried out to investigate if 2H, 13C, 15N and 18O stable isotope signatures could be used in conjunction with multivariate chemometric data analysis to determine potential linkage between benzocaine exhibits seized from different locations or individuals to assist with investigation and prosecution of drug

  4. Femtosecond Laser Ablation Multicollector ICPMS Analysis of Uranium Isotopes in NIST Glass

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

    Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.

    We have utilized femtosecond laser ablation coupled to multi-collector inductively couple plasma mass spectrometry to measure the uranium isotopic content of NIST 61x (x=0,2,4,6) glasses. The uranium content of these glasses is a linear two-component mixing between isotopically natural uranium and the isotopically depleted spike used in preparing the glasses. Laser ablation results match extremely well, generally within a few ppm, with solution analysis following sample dissolution and chemical separation. In addition to isotopic data, sample utilization efficiency measurements indicate that over 1% of ablated uranium atoms reach a mass spectrometer detector, making this technique extremely efficient. Laser sampling alsomore » allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.« less

  5. C-isotope composition of fossil sedges and grasses

    NASA Astrophysics Data System (ADS)

    Kurschner, Wolfram M.

    2010-05-01

    C4 plants differ from C3 plants regarding their anatomy and their C-isotope composition. Both features can be used in the geological record to determine the presence of C4 plants. Yet, the evolution of the C4 pathway in the fossil record is enigmatic as palaeobotanical and geological evidence for C4 plants is sparse. The oldest structural evidence for Kranz anatomy has been found in Late Miocene permineralized grass leaf remains. But studies on the C-isotope composition of sedimentary organic matter indicate that abundant C4 biomass was present in N-America and Asia throughout the Miocene in expanding savannahs and grasslands. The success of C4 plants appears to be related also to an increasing seasonal aridity in the tropical climate belts and the co-evolution of grazers. However, C- isotope composition of palaeosols or vertebrate teeth only allows to estimate the abundance of C4 plant biomass in the vegetation or in the diet without further taxonomical specification which plant groups would have had C4 metabolism. In this contribution the first extensive C-isotope analysis of fossil seeds of sedges and a few grasses are presented. The age of the carpological material ranges from Late Eocene to Pliocene and was collected from several central European brown coal deposits. The 52 different taxa studied include several species of Carex, Cladiocarya, Eriopherum, Eleocharis, Scirpus, Sparganium. Most of them representing herbaceous elements of a (sub)tropical vegetation growing near the edge of a lake. The C-isotope composition of the fossil seeds varies between -30 and -23 o/oo indicating C3 photosynthesis. This first systematic inventory shows that C4 plants were absent in the European (sub)tropical brown coal forming wetland vegetation during the Tertiary. These preliminary data are in agreement with phylogenetic studies which predict the origin of C4 plants outside the European realm.

  6. Screening molecular associations with lipid membranes using natural abundance 13C cross-polarization magic-angle spinning NMR and principal component analysis.

    PubMed

    Middleton, David A; Hughes, Eleri; Madine, Jillian

    2004-08-11

    We describe an NMR approach for detecting the interactions between phospholipid membranes and proteins, peptides, or small molecules. First, 1H-13C dipolar coupling profiles are obtained from hydrated lipid samples at natural isotope abundance using cross-polarization magic-angle spinning NMR methods. Principal component analysis of dipolar coupling profiles for synthetic lipid membranes in the presence of a range of biologically active additives reveals clusters that relate to different modes of interaction of the additives with the lipid bilayer. Finally, by representing profiles from multiple samples in the form of contour plots, it is possible to reveal statistically significant changes in dipolar couplings, which reflect perturbations in the lipid molecules at the membrane surface or within the hydrophobic interior.

  7. Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

    PubMed

    Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. In-Gel Stable-Isotope Labeling (ISIL): a strategy for mass spectrometry-based relative quantification.

    PubMed

    Asara, John M; Zhang, Xiang; Zheng, Bin; Christofk, Heather H; Wu, Ning; Cantley, Lewis C

    2006-01-01

    Most proteomics approaches for relative quantification of protein expression use a combination of stable-isotope labeling and mass spectrometry. Traditionally, researchers have used difference gel electrophoresis (DIGE) from stained 1D and 2D gels for relative quantification. While differences in protein staining intensity can often be visualized, abundant proteins can obscure less abundant proteins, and quantification of post-translational modifications is difficult. A method is presented for quantifying changes in the abundance of a specific protein or changes in specific modifications of a protein using In-gel Stable-Isotope Labeling (ISIL). Proteins extracted from any source (tissue, cell line, immunoprecipitate, etc.), treated under two experimental conditions, are resolved in separate lanes by gel electrophoresis. The regions of interest (visualized by staining) are reacted separately with light versus heavy isotope-labeled reagents, and the gel slices are then mixed and digested with proteases. The resulting peptides are then analyzed by LC-MS to determine relative abundance of light/heavy isotope pairs and analyzed by LC-MS/MS for identification of sequence and modifications. The strategy compares well with other relative quantification strategies, and in silico calculations reveal its effectiveness as a global relative quantification strategy. An advantage of ISIL is that visualization of gel differences can be used as a first quantification step followed by accurate and sensitive protein level stable-isotope labeling and mass spectrometry-based relative quantification.

  9. Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on the isotope values.

    PubMed

    Dutra, S V; Adami, L; Marcon, A R; Carnieli, G J; Roani, C A; Spinelli, F R; Leonardelli, S; Vanderlinde, R

    2013-12-01

    We studied Brazilian wines produced by microvinification from Cabernet Sauvignon and Merlot grapes, vintages 2007 and 2008, from the Serra Gaúcha, Campanha and Serra do Sudeste regions, in order to differentiate them according to geographical origin by using isotope and mineral element analyses. In addition, the influence of vintage production in isotope values was verified. Isotope analysis was performed by isotope ratio mass spectrometry (IRMS), and the determination of minerals was by flame atomic absorption (FAA). The best parameters to classify the wines in the 2008 vintage were Rb and Li. The results of the δ(13)C of wine ethanol, Rb and Li showed a significant difference between the varieties regardless of the region studied. The δ(18)O values of water and δ(13)C of ethanol showed significant differences, regardless of the variety. Discriminant analysis of isotope and minerals values allowed to classify approximately 80% of the wines from the three regions studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Stable isotope ratio mass spectrometry of nanogram quantities of boron and sulfur

    NASA Astrophysics Data System (ADS)

    Wieser, Michael Eugene

    1998-09-01

    Instrumentation and analytical techniques were developed to measure isotope abundances from nanograms of sulfur and boron. Sulfur isotope compositions were determined employing continuous flow isotope ratio mass spectroscopy (CF-IRMS) procedures and AsS+ thermal ionization mass spectrometry techniques (AsS+-TIMS). Boron isotope abundances were determined by BO2/sp--TIMS. CF-IRMS measurements realized δ34S values from 10 μg sulfur with precisions of ±0.3/perthous. To extend sulfur isotope measurements to much smaller samples, a TIMS procedure was developed to measure 75As32S+ and 75As34S+ at masses 108 and 109 from 200 ng S on a Finnigan MAT 262 with an ion counter. This is possibly the smallest amount of sulfur which has been successfully analyzed isotopically. The internal precision of 32S/34S ratios measured by AsS+-TIMS was better than ±0.15 percent. δ34S-values calculated relative to the measured 32S/34S value of an IAEA AG2S standard (S-1) agreed with those determined by CF-IRMS to within ±3/perthous. The increasing sensitivity of S-isotope analyses permits hiterto impossible investigations e.g. sulfur in tree rings and ice cores. Boron isotope abundances were measured as BO2/sp- from 50 ng B using an older thermal ionization mass spectrometer which had been extensively upgraded including the addition of computer control electronics, sensitive ion current amplification and fiber optic data bus. The internal precisions of the measured 11B/10B ratios were ±0.15 percent and the precisions of δ11B values calculated relative to the accepted international standard (SRM-951) were ±3/perthous. Two applications of boron isotope abundance variations were initiated (1) ground waters of Northern Alberta and (2) coffee beans in different regions of the world. In the first it was demonstrated that boron isotopes could be used to trace boron released during steam injection of oil sands into the surrounding environment. Data from the second study suggest that boron

  11. Carbon-isotopic analysis of individual pollen grains from C 3 and C 4 grasses using a spooling-wire microcombustion interface

    NASA Astrophysics Data System (ADS)

    Nelson, David M.; Hu, Feng Sheng; Mikucki, Jill A.; Tian, Jian; Pearson, Ann

    2007-08-01

    Pollen grains from grasses using the C 3 and C 4 photosynthetic pathways have distinct ranges of δ 13C values that may be used to estimate their relative abundance in paleorecords. We evaluated a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer (SWiM-IRMS) for δ 13C analysis of individual grass-pollen grains. Pollen from four C 3 and four C 4 grass species was isolated through micromanipulation and analyzed as single grains suspended in water. A carbon yield greater than the 2 σ range of the carbon content of blanks containing only water was used to distinguish samples containing pollen ("pollen present") from those not containing pollen. This criterion resulted in the exclusion of ˜45% of the 946 samples applied to the wire. The average δ 13C values (±1 σ) of the remaining samples were -26.9‰ (±6.3‰) and -11.5‰ (±9.6‰) for C 3 grasses and C 4 grasses, respectively, after blank-correcting the δ 13C data. These results suggest that the SWiM-IRMS system can be used to distinguish C 3 from C 4 grass pollen. The high variability in measured δ 13C values is likely caused by a combination of factors. These include natural isotopic variability among individual pollen grains; the relatively poor precision that can be obtained when determining δ 13C values of such small samples; and the uncertainty in the magnitude, isotopic composition, and stability of the analytical blank. Nonetheless, high percentages of individual pollen grains were correctly classified as being of either C 3 or C 4 origin. On average, 90% (range = 78-100%) of pollen grains from C 3 grasses had δ 13C values more negative than the cutoff threshold of -19.2‰; while 84% (range = 77-90%) of pollen grains from C 4 grasses had δ 13C values more positive than -19.2‰. Compared with analysis using an elemental analyzer interfaced with an IRMS (EA-IRMS), the number of pollen grains required for δ 13C-based evaluation of C 3/C 4 grass composition

  12. Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes

    EPA Science Inventory

    Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...

  13. Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

    2017-04-01

    In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

  14. Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy

    NASA Astrophysics Data System (ADS)

    Hu, Zhongya; Hu, Wenxuan; Wang, Xiaomin; Lu, Yizhou; Wang, Lichao; Liao, Zhiwei; Li, Weiqiang

    2017-07-01

    Magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates. Calcite, due to its ubiquitous occurrence and the large Mg isotope fractionation associated with the mineral, has attracted great interests in applications of Mg isotope geochemistry. However, the fidelity of Mg isotopes in geological records of carbonate minerals (e.g., calcite and dolomite) against burial metamorphism remains poorly constrained. Here we report our investigation on the Mg isotope systematics of a dolomitized Middle Triassic Geshan carbonate section in eastern China. Magnesium isotope analysis was complemented by analyses of Sr-C-O isotopic compositions, major and trace element concentrations, and petrographic and mineralogical features. Multiple lines of evidence consistently indicated that post-depositional diagenesis of carbonate minerals occurred to the carbonate rocks. Magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high δ26Mg dolomite end member and a low δ26Mg calcite end member, irrespective of sample positions in the section and calcite/dolomite ratio in the samples. By fitting the measured Mg isotope data using a two-end member mixing model, an inter-mineral Δ26Mgdolomite-calcite fractionation of 0.72‰ was obtained. Based on the experimentally derived Mg isotope fractionation factors for dolomite and calcite, a temperature of 150-190 °C was calculated to correspond to the 0.72‰ Δ26Mgdolomite-calcite fractionation. Such temperature range matches with the burial-thermal history of the local strata, making a successful case of Mg isotope geothermometry. Our results indicate that both calcite and dolomite had been re-equilibrated during burial metamorphism, and based on isotope mass balance of Mg, the system was buffered by dolomite in the section. Therefore, burial metamorphism may reset Mg isotope signature of calcite, and Mg isotope compositions in calcite should be dealt with caution in

  15. Silicon isotope amount ratios and molar masses for two silicon isotope reference materials: IRMM-018a and NBS28

    NASA Astrophysics Data System (ADS)

    Valkiers, S.; Ding, T.; Inkret, M.; Ruße, K.; Taylor, P.

    2005-04-01

    A new 2 kg batch of SiO2 crystals, IRMM-018a as well as the existing NBS28 silica sand (or RM 8546, obtained by I. Friedman from U.S. Geological Survey) have been characterised for their "absolute" silicon isotope composition and molar mass. The amount-of-substance measurements needed for that purpose were performed on the IRMM amount comparator (Avogadro II) on samples from these batches, which were converted to gaseous silicon tetra-fluoride (SiF4). The isotope amount ratio measurements were calibrated by means of synthesized isotope amount ratios realized in the form of synthetic Si isotope mixtures, the measurement procedure of which makes them SI-traceable. IRMM-018a is intended to be used as Isotope Reference Material for isotope amount measurements in geochemical and other isotope abundance studies of silicon. It is distributed in samples of about 0.1 mol and will replace IRMM-018 (exhausted).

  16. 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

  17. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

    PubMed Central

    Larsen, K.K.; Wielandt, D.; Schiller, M.; Bizzarro, M.

    2016-01-01

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that

  18. Stable Isotopes, Quantum Computing and Consciousness

    NASA Astrophysics Data System (ADS)

    Berezin, Alexander A.

    2000-10-01

    Recent proposals of quantum computing/computers (QC) based on nuclear spins suggest that consciousness (CON) activity may be related (assisted) to subset of C13 atoms incorporated randomly, or quasirandomly, in neural structures. Consider two DNA chains. Even if they are completely identical chemically (same sequence of codons), patterns of 12C and 13C isotopes in them are different (possible origin of personal individuality). Perhaps it is subsystem of nuclear spins of 13C "sublattice" which forms dynamical system capable of QC and on which CON is "spanned". Some issues related to this hypothesis are: (1) existence of CON-driven positional correlations among C13 atoms, (2) motion (hopping) of C13 via enhanced neutron tunneling, cf. quantum "anti Zeno-effect", (3) possible optimization of concentration of QC-active C13 atoms above their standard isotopic abundance, (4) characteristic time-scales for operation of C13-based QC (perrhaps, broad range of scales), (5) reflection of QC dynamics of C13 on CON, (6) possibility that C13-based QC operates "above" level of "regular" CON (perhaps, Jungian sub/super-CON), (7) isotopicity as connector to universal Library of Patterns ("Platonic World"), (8) self-stabilization of coherence in C13 (sub)system. Some of this questions are, in principle, experimentally addressable through shifting of isotopic abundances.

  19. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

    An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

  20. Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

    USGS Publications Warehouse

    Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

    2002-01-01

    Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among

  1. Spectral analysis software improves confidence in plant and soil water stable isotope analyses performed by isotope ratio infrared spectroscopy (IRIS).

    PubMed

    West, A G; Goldsmith, G R; Matimati, I; Dawson, T E

    2011-08-30

    Previous studies have demonstrated the potential for large errors to occur when analyzing waters containing organic contaminants using isotope ratio infrared spectroscopy (IRIS). In an attempt to address this problem, IRIS manufacturers now provide post-processing spectral analysis software capable of identifying samples with the types of spectral interference that compromises their stable isotope analysis. Here we report two independent tests of this post-processing spectral analysis software on two IRIS systems, OA-ICOS (Los Gatos Research Inc.) and WS-CRDS (Picarro Inc.). Following a similar methodology to a previous study, we cryogenically extracted plant leaf water and soil water and measured the δ(2)H and δ(18)O values of identical samples by isotope ratio mass spectrometry (IRMS) and IRIS. As an additional test, we analyzed plant stem waters and tap waters by IRMS and IRIS in an independent laboratory. For all tests we assumed that the IRMS value represented the "true" value against which we could compare the stable isotope results from the IRIS methods. Samples showing significant deviations from the IRMS value (>2σ) were considered to be contaminated and representative of spectral interference in the IRIS measurement. Over the two studies, 83% of plant species were considered contaminated on OA-ICOS and 58% on WS-CRDS. Post-analysis, spectra were analyzed using the manufacturer's spectral analysis software, in order to see if the software correctly identified contaminated samples. In our tests the software performed well, identifying all the samples with major errors. However, some false negatives indicate that user evaluation and testing of the software are necessary. Repeat sampling of plants showed considerable variation in the discrepancies between IRIS and IRMS. As such, we recommend that spectral analysis of IRIS data must be incorporated into standard post-processing routines. Furthermore, we suggest that the results from spectral analysis be

  2. Tracking the weathering of basalts on Mars using lithium isotope fractionation models

    PubMed Central

    Losa‐Adams, Elisabeth; Gil‐Lozano, Carolina; Gago‐Duport, Luis; Uceda, Esther R.; Squyres, Steven W.; Rodríguez, J. Alexis P.; Davila, Alfonso F.; McKay, Christopher P.

    2015-01-01

    Abstract Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt‐forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history. PMID:27642264

  3. Application of stable isotope ratio analysis for biodegradation monitoring in groundwater

    USGS Publications Warehouse

    Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

    2013-01-01

    Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions.

  4. Meteorites and their parent bodies: Evidence from oxygen isotopes

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.

    1978-01-01

    Isotopic abundance variations among meteorites are used to establish genetic associations between meteorite classes. Oxygen isotope distributions between group II E irons with H-group ordinary chondrites and enstatic meteorites indicate that the parent bodies were formed out of pre-solar material that was not fully mixed at the time condensation occurred within the solar nebula.

  5. 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

  6. Measurement of isotope ratio of Ca{sup +} ions in a linear Paul Trap

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

    Hashimoto, Y.; Minamino, K.; Nagamoto, D.

    2009-03-17

    Measurement of isotope ratios of Calcium is very useful in many fields. So we demonstrated the measurement of isotope ratios of {sup 40}Ca{sup +}(abundance 96.4%) to {sup 44}Ca{sup +}(2.09%) ions in a linear Paul trap with several laser lights tuning to the isotope shifts. And we found that the experimental parameters had large influences on the measurement of the isotope ratios.

  7. Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

    NASA Astrophysics Data System (ADS)

    Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

    2013-12-01

    Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary

  8. Triple oxygen isotope analysis of tropospheric CO2 on the two sides of the Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Liang, M. C.; Newman, S.; Laskar, A. H.

    2017-12-01

    The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, stratospheric photochemistry, cross-tropopause exchange, and subsequent vertical mixing between the free troposphere and planetary boundary. Oxygen isotopes, in particular, are affected by both the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516 ln(1+d18O)) provides a powerful constraint on the strengths of the associated cycles involving CO2. Here, we report and compare summer to winter seasons CO2 isotopic composition from Taiwan (Taipei) and USA (Palos Verdes, CA). On average, the D17O values from Taiwan are significantly higher than those in USA. Analysis shows that the impact of 2014-2016 El Nino event on the observed D17O values is not visible, in contrast to what was reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Attempts are made to understand the elevated D17O values in the eastern Pacific compared to those in the western Pacific. Implications for utilizing the new tracer D17O along with the conventional d18O for carbon cycling studies are also discussed.

  9. Discrimination of ginseng cultivation regions using light stable isotope analysis.

    PubMed

    Kim, Kiwook; Song, Joo-Hyun; Heo, Sang-Cheol; Lee, Jin-Hee; Jung, In-Woo; Min, Ji-Sook

    2015-10-01

    Korean ginseng is considered to be a precious health food in Asia. Today, thieves frequently compromise ginseng farms by pervasive theft. Thus, studies regarding the characteristics of ginseng according to growth region are required in order to deter ginseng thieves and prevent theft. In this study, 6 regions were selected on the basis of Korea regional criteria (si, gun, gu), and two ginseng-farms were randomly selected from each of the 6 regions. Then 4-6 samples of ginseng were acquired from each ginseng farm. The stable isotopic compositions of H, O, C, and N of the collected ginseng samples were analyzed. As a result, differences in the hydrogen isotope ratios could be used to distinguish regional differences, and differences in the nitrogen isotope ratios yielded characteristic information regarding the farms from which the samples were obtained. Thus, stable isotope values could be used to differentiate samples according to regional differences. Therefore, stable isotope analysis serves as a powerful tool to discriminate the regional origin of Korean ginseng samples from across Korea. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  10. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    USGS Publications Warehouse

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  11. Stable isotopes in juvenile marine fishes and their invertebrate prey from the Thames Estuary, UK, and adjacent coastal regions

    NASA Astrophysics Data System (ADS)

    Leakey, Chris D. B.; Attrill, Martin J.; Jennings, Simon; Fitzsimons, Mark F.

    2008-04-01

    Estuaries are regarded as valuable nursery habitats for many commercially important marine fishes, potentially providing a thermal resource, refuge from predators and a source of abundant prey. Stable isotope analysis may be used to assess relative resource use from isotopically distinct sources. This study comprised two major components: (1) development of a spatial map and discriminant function model of stable isotope variation in selected invertebrate groups inhabiting the Thames Estuary and adjacent coastal regions; and (2) analysis of stable isotope signatures of juvenile bass ( Dicentrarchus labrax), sole ( Solea solea) and whiting ( Merlangius merlangus) for assessment of resource use and feeding strategies. The data were also used to consider anthropogenic enrichment of the estuary and potential energetic benefits of feeding in estuarine nursery habitat. Analysis of carbon (δ 13C), nitrogen (δ 15N) and sulphur (δ 34S) isotope data identified significant differences in the 'baseline' isotopic signatures between estuarine and coastal invertebrates, and discriminant function analysis allowed samples to be re-classified to estuarine and coastal regions with 98.8% accuracy. Using invertebrate signatures as source indicators, stable isotope data classified juvenile fishes to the region in which they fed. Feeding signals appear to reflect physiological (freshwater tolerance) and functional (mobility) differences between species. Juvenile sole were found to exist as two isotopically-discrete sub-populations, with no evidence of mixing between the two. An apparent energetic benefit of estuarine feeding was only found for sole.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  13. Stable carbon and nitrogen isotope analysis of avian uric acid.

    PubMed

    Bird, Michael I; Tait, Elaine; Wurster, Christopher M; Furness, Robert W

    2008-11-01

    We report results obtained using a new technique developed to measure the stable-isotope composition of uric acid isolated from bird excreta (guano). Results from a diet-switch feeding trial using zebra finches suggest that the delta(13)C of uric acid in the guano equilibrates with the diet of the bird within 3 days of a change in diet, while the equilibration time for delta(15)N may be longer. The average carbon isotope discrimination between uric acid and food before the diet switch was +0.34 +/- 1 per thousand (1sigma) while after the diet switch this increased slightly to +0.83 +/- 0.7 per thousand (1sigma). Nitrogen isotope discrimination was +1.3 +/- 0.3 per thousand (1sigma) and +0.3 +/- 0.3 per thousand (1sigma) before and after the diet switch; however, it is possible that the nitrogen isotope values did not fully equilibrate with diet switch over the course of the experiment. Analyses of other chemical fractions of the guano (organic residue after uric acid extraction and non-uric acid organics solubilised during extraction) suggest a total range of up to 3 per thousand for both delta(13)C and delta(15)N values in individual components of a single bulk guano sample. The analysis of natural samples from a range of terrestrial and marine species demonstrates that the technique yields isotopic compositions consistent with the known diets of the birds. The results from natural samples further demonstrate that multiple samples from the same species collected from the same location yield similar results, while different species from the same location exhibit a range of isotopic compositions indicative of different dietary preferences. Given that many samples of guano can be rapidly collected without any requirement to capture specimens for invasive sampling, the stable-isotope analysis of uric acid offers a new, simple and potentially powerful tool for studying avian ecology and metabolism.

  14. Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

    PubMed

    Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

    2013-12-01

    Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Improvements in the MGA Code Provide Flexibility and Better Error Analysis

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

    Ruhter, W D; Kerr, J

    2005-05-26

    The Multi-Group Analysis (MGA) code is widely used to determine nondestructively the relative isotopic abundances of plutonium by gamma-ray spectrometry. MGA users have expressed concern about the lack of flexibility and transparency in the code. Users often have to ask the code developers for modifications to the code to accommodate new measurement situations, such as additional peaks being present in the plutonium spectrum or expected peaks being absent. We are testing several new improvements to a prototype, general gamma-ray isotopic analysis tool with the intent of either revising or replacing the MGA code. These improvements will give the user themore » ability to modify, add, or delete the gamma- and x-ray energies and branching intensities used by the code in determining a more precise gain and in the determination of the relative detection efficiency. We have also fully integrated the determination of the relative isotopic abundances with the determination of the relative detection efficiency to provide a more accurate determination of the errors in the relative isotopic abundances. We provide details in this paper on these improvements and a comparison of results obtained with current versions of the MGA code.« less

  16. Quantifying inter-laboratory variability in stable isotope analysis of ancient skeletal remains.

    PubMed

    Pestle, William J; Crowley, Brooke E; Weirauch, Matthew T

    2014-01-01

    Over the past forty years, stable isotope analysis of bone (and tooth) collagen and hydroxyapatite has become a mainstay of archaeological and paleoanthropological reconstructions of paleodiet and paleoenvironment. Despite this method's frequent use across anthropological subdisciplines (and beyond), the present work represents the first attempt at gauging the effects of inter-laboratory variability engendered by differences in a) sample preparation, and b) analysis (instrumentation, working standards, and data calibration). Replicate analyses of a 14C-dated ancient human bone by twenty-one archaeological and paleoecological stable isotope laboratories revealed significant inter-laboratory isotopic variation for both collagen and carbonate. For bone collagen, we found a sizeable range of 1.8‰ for δ13Ccol and 1.9‰ for δ15Ncol among laboratories, but an interpretatively insignificant average pairwise difference of 0.2‰ and 0.4‰ for δ13Ccol and δ15Ncol respectively. For bone hydroxyapatite the observed range increased to a troublingly large 3.5‰ for δ13Cap and 6.7‰ for δ18Oap, with average pairwise differences of 0.6‰ for δ13Cap and a disquieting 2.0‰ for δ18Oap. In order to assess the effects of preparation versus analysis on isotopic variability among laboratories, a subset of the samples prepared by the participating laboratories were analyzed a second time on the same instrument. Based on this duplicate analysis, it was determined that roughly half of the isotopic variability among laboratories could be attributed to differences in sample preparation, with the other half resulting from differences in analysis (instrumentation, working standards, and data calibration). These findings have serious implications for choices made in the preparation and extraction of target biomolecules, the comparison of results obtained from different laboratories, and the interpretation of small differences in bone collagen and hydroxyapatite isotope values

  17. Quantifying Inter-Laboratory Variability in Stable Isotope Analysis of Ancient Skeletal Remains

    PubMed Central

    Pestle, William J.; Crowley, Brooke E.; Weirauch, Matthew T.

    2014-01-01

    Over the past forty years, stable isotope analysis of bone (and tooth) collagen and hydroxyapatite has become a mainstay of archaeological and paleoanthropological reconstructions of paleodiet and paleoenvironment. Despite this method's frequent use across anthropological subdisciplines (and beyond), the present work represents the first attempt at gauging the effects of inter-laboratory variability engendered by differences in a) sample preparation, and b) analysis (instrumentation, working standards, and data calibration). Replicate analyses of a 14C-dated ancient human bone by twenty-one archaeological and paleoecological stable isotope laboratories revealed significant inter-laboratory isotopic variation for both collagen and carbonate. For bone collagen, we found a sizeable range of 1.8‰ for δ13Ccol and 1.9‰ for δ15Ncol among laboratories, but an interpretatively insignificant average pairwise difference of 0.2‰ and 0.4‰ for δ13Ccol and δ15Ncol respectively. For bone hydroxyapatite the observed range increased to a troublingly large 3.5‰ for δ13Cap and 6.7‰ for δ18Oap, with average pairwise differences of 0.6‰ for δ13Cap and a disquieting 2.0‰ for δ18Oap. In order to assess the effects of preparation versus analysis on isotopic variability among laboratories, a subset of the samples prepared by the participating laboratories were analyzed a second time on the same instrument. Based on this duplicate analysis, it was determined that roughly half of the isotopic variability among laboratories could be attributed to differences in sample preparation, with the other half resulting from differences in analysis (instrumentation, working standards, and data calibration). These findings have serious implications for choices made in the preparation and extraction of target biomolecules, the comparison of results obtained from different laboratories, and the interpretation of small differences in bone collagen and hydroxyapatite isotope values

  18. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

    PubMed

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

    2016-04-22

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a

  19. Cross-continental triple oxygen isotope analysis of tropospheric CO2

    NASA Astrophysics Data System (ADS)

    Liang, M. C.; Rangarajan, R.; Newman, S.; Laskar, A. H.

    2016-12-01

    The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516´ln(1+d18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

  20. Application of Natural Isotopic Abundance ¹H-¹³C- and ¹H-¹⁵N-Correlated Two-Dimensional NMR for Evaluation of the Structure of Protein Therapeutics.

    PubMed

    Arbogast, Luke W; Brinson, Robert G; Marino, John P

    2016-01-01

    Methods for characterizing the higher-order structure of protein therapeutics are in great demand for establishing consistency in drug manufacturing, for detecting drug product variations resulting from modifications in the manufacturing process, and for comparing a biosimilar to an innovator reference product. In principle, solution NMR can provide a robust approach for characterization of the conformation(s) of protein therapeutics in formulation at atomic resolution. However, molecular weight limitations and the perceived need for stable isotope labeling have to date limited its practical applications in the biopharmaceutical industry. Advances in NMR magnet and console technologies, cryogenically cooled probes, and new rapid acquisition methodologies, particularly selective optimized flip-angle short transient pulse schemes and nonuniform sampling, have greatly ameliorated these limitations. Here, we describe experimental methods for the collection and analysis of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra applied to protein drug products at natural isotopic abundance, including representatives from the rapidly growing class of monoclonal antibody (mAb) therapeutics. Practical aspects of experimental setup and data acquisition for both standard and rapid acquisition NMR techniques are described. Furthermore, strategies for the statistical comparison of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra are detailed. 2016 Published by Elsevier Inc.

  1. Abundance and isotope systematics of carbon in subglacial basalts, geothermal gases and fluids from Iceland's rift zones

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Fueri, E.; Halldorsson, S. A.; Fischer, T. P.; Gronvold, K.

    2010-12-01

    P. H. BARRY1*, D. R. HILTON1, E. FÜRI1, S.A. HALLDÓRSON1, T.P. FISCHER2, K. GRONVOLD3 1 Scripps Institution of Oceanography, UCSD, La Jolla, California 92093, USA (*Correspondence: pbarry@ucsd.edu). 2University of New Mexico, Albuquerque, NM 87131, USA. 3University of Iceland, Askja, Sturlugata 7, IS-101, Reykjavik, Iceland Carbon dioxide (CO2) is the dominant non-aqueous volatile species found in oceanic basalts and geothermal fluids and serves as the carrier gas for trace volatiles such as He and other noble gases. The aim of this study is to identify the superimposed effects of degassing and crustal contamination on the CO2 systematics of the Icelandic hotspot in order to reveal and characterize the carbon abundance and isotopic features of the underlying mantle source. Our approach involves coupling CO2 with He, utilizing the sensitivity of 3He/4He ratios to reveal mantle and crustal inputs. We report new C-isotope (δ13C) and abundance characteristics for a suite of 47 subglacial basalts and 50 geothermal gases and fluids from Iceland. CO2 contents in hyaloclastite glasses are extremely low (10-100 ppm) and likely residual following extensive degassing whereas geothermal fluids are dominated by CO2 (>90 %). C-isotopes range from -27.2 to -3.6 ‰ (vs. PDB) for basalts and from -18.8 to 2.86 ‰ (vs. PDB) for geothermal samples (mean = -4.2 ± 3.6 ‰). CO2/3He ratios range from 108 to 1012 for basalts and from 105 to 1012 for geothermal samples: In both cases, our results extend He-CO2 relationships over a much broader range than reported previously [1]. Taken together, these data suggest that several processes including mixing, degassing, and/or syn- or post-eruptive crustal contamination may act to modify CO2 source characteristics. Equilibrium degassing models are compatible with ~75 % of the basalt data, and preliminary results indicate that initial Icelandic source characteristics are ~500 ppm CO2 and δ13C ~ -5 ‰ (vs. PDB). These values are high

  2. High resolution and high precision on line isotopic analysis of Holocene and glacial ice performed in the field

    NASA Astrophysics Data System (ADS)

    Gkinis, V.; Popp, T. J.; Johnsen, S. J.; Blunier, T.; Bigler, M.; Stowasser, C.; Schüpbach, S.; Leuenberger, D.

    2010-12-01

    Ice core records as obtained from polar ice caps provide a wealth of paleoclimatic information. One of the main features of ice cores is their potential for high temporal resolution. The isotopic signature of the ice, expressed through the relative abundances of the two heavy isotopologues H218O and HD16O, is a widely used proxy for the reconstruction of past temperature and accumulation. One step further the combined information obtained from these two isotopologues, commonly referred to as the deuterium excess, can be utilized to infer additional information about the source of the precipitated moisture. Until very recently isotopic analysis of polar ice was performed with isotope Ratio Mass Spectrometry (IRMS) in a discrete fashion resulting in a high workload related to the preparation of samples. Most important though the available temporal resolution of the ice core was in many cases not fully exploited. In order to overcome these limitations we have developed a system that interfaces a commercially available IR laser cavity ring-down spectrometer tailored for water isotope analysis to a stream of liquid water as extracted from a continuously melted ice rod. The system offers the possibility for simultaneous δ18O and δD analysis with a sample requirement of approximately 0.1 ml/min. The system has been deployed in the field during the NEEM ice core drilling project on 2009 and 2010. In this study we present actual on line measurements of Holocene and glacial ice. We also discuss how parameters as the melt rate, acquisition rate and integration time affect the obtained precision and resolution and we describe data analysis techniques that can improve these last two parameters. By applying spectral methods we are able to quantify the smoothing effects imposed by diffusion of the sample in the sample transfer lines and the optical cavity of the instrument. We demonstrate that with an acquisition rate of 0.2 Hz we are able to obtain a precision of 0.5‰ and 0

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

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

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

  4. Variability in the carbon isotope composition of individual amino acids in plant proteins from different sources: 1 Leaves.

    PubMed

    Lynch, Anthony H; Kruger, Nicholas J; Hedges, Robert E M; McCullagh, James S O

    2016-05-01

    The natural carbon isotope composition of individual amino acids from plant leaf proteins has been measured to establish potential sources of variability. The plant leaves studied, taken from a range of plant groups (forbs, trees, grasses, and freshwater aquatic plants), showed no significant influence of either season or environment (water and light availability) on their Δδ(13)C values. Plant groups did, however, differ in carbon isotope composition, although no consistent differences were identified at the species level. A discriminant analysis model was constructed which allowed leaves from (1) nettles, (2) Pooideae, (3) other Poales, (4) trees and (5) freshwater higher plants to be distinguished from each other on the basis of their natural abundance (13)C/(12)C ratios of individual amino acids. Differences in carbon isotope composition are known to be retained, to some extent, in the tissues of their consumers, and hence an understanding of compound-specific variation in (13)C/(12)C fractional abundance in plants has the potential to provide dietary insights of value in archaeological and ecological studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Zircon (Hf, O isotopes) as melt indicator: Melt infiltration and abundant new zircon growth within melt rich layers of granulite-facies lenses versus solid-state recrystallization in hosting amphibolite-facies gneisses (central Erzgebirge, Bohemian Massif)

    NASA Astrophysics Data System (ADS)

    Tichomirowa, Marion; Whitehouse, Martin; Gerdes, Axel; Schulz, Bernhard

    2018-03-01

    In the central Erzgebirge within the Bohemian Massif, lenses of high pressure and ultrahigh pressure felsic granulites occur within meta-sedimentary and meta-igneous amphibolite-facies felsic rocks. In the felsic granulite, melt rich parts and restite form alternating layers, and were identified by petrology and bulk rock geochemistry. Mineral assemblages representing the peak P-T conditions were best preserved in melanocratic restite layers. In contrast, in the melt rich leucocratic layers, garnet and related HP minerals as kyanite are almost completely resorbed. Both layers display differences in accessory minerals: melanosomes have frequent and large monazite and Fe-Ti-minerals but lack xenotime and apatite; leucosomes have abundant apatite and xenotime while monazite is rare. Here we present a detailed petrographic study of zircon grains (abundance, size, morphology, inclusions) in granulite-facies and amphibolite-facies felsic gneisses, along with their oxygen and hafnium isotope compositions. Our data complement earlier Usbnd Pb ages and trace element data (REE, Y, Hf, U) on zircons from the same rocks (Tichomirowa et al., 2005). Our results show that the degree of melting determines the behaviour of zircon in different layers of the granulites and associated amphibolite-facies rocks. In restite layers of the granulite lenses, small, inherited, and resorbed zircon grains are preserved and new zircon formation is very limited. In contrast, new zircons abundantly grew in the melt rich leucocratic layers. In these layers, the new zircons (Usbnd Pb age, trace elements, Hf, O isotopes) best preserve the information on peak metamorphic conditions due to intense corrosion of other metamorphic minerals. The new zircons often contain inherited cores. Compared to cores, the new zircons and rims show similar or slightly lower Hf isotope values, slightly higher Hf model ages, and decreased oxygen isotope ratios. The isotope compositions (Hf, O) of new zircons indicate

  6. Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Franz, H. B.; Mahaffy, P. R.; Stern, J.; Archer, P., Jr.; Conrad, P.; Eigenbrode, J.; Freissinet, C.; Glavin, D.; Grotzinger, J. P.; Jones, J.; hide

    2015-01-01

    In October 2014, the Mars Science Laboratory (MSL) "Curiosity" rover drilled into the sediment at the base of Mount Sharp in a location namsed Cionfidence Hills (CH). CH marked the fifth sample pocessed by the Sample Analysis at Mars (SAM) instrument suite since Curiosity arrived in Gale Crater, with previous analyses performed at Rocknest (RN), John Klein (JK), Cumberland (CB), and Windjana (WJ). Evolved gas analysis (EGA) of all samples has indicated H2O as well as O-, C- and S-bearing phases in the samples, often at abundances that would be below the detection limit of the CheMin instrument. By examining the temperatures at which gases are evolved from samples, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases when their identities are unclear to CheMin. SAM may also detect gases evolved from amorphous material in solid samples, which is not suitable for analysis by CheMin. Finally, the isotopic composition of these gases may suggest possible formation scenarios and relationships between phases. We will discuss C isotope ratios of CO2 evolved from the CH sample as measured with SAM's quadrupole mass spectrometer (QMS) and draw comparisons to samples previously analyzed by SAM.

  7. Rb-Sr systematics and REE abundances in Shalka and several other diogenites

    NASA Astrophysics Data System (ADS)

    Takahashi, K.; Yabuki, S.; Kagi, H.; Masuda, A.

    1994-07-01

    The diogenites have been regarded as igneous products in the early solar system and they have been considered to have genetically close relationship with eucrites. Depsite their simple mineralogical compositions and narrow range for major-element compositions, diogenites have been known to show wide Rare Earth Elements (REE) variations in absolute concentration and in mutual abundance ratios. Furthermore, some diogenites have peculiar Rb-Sr isotope systematics (ages younger than 4.5 b.y.). The Shalka meteorite belongs to the diogenites, and a unique REE abundance pattern has been reported. We performed Rb-Sr isotopic analyses and measured REE abundances in the Shalka diogenite with several other diogenites to discuss their genesis. Roughly speaking, REE patterns in diogenites are characterized by the negative Eu anomaly and the depletion of light REE. For Shalka, some heterogeneity in REE abundance patterns have been observed. While one sample chip shows the REE pattern with a large negative Eu anomaly and depleted light REE, particularly characterized by the concave curvature for the La-Nd span, other samples show the pattern nearly flat or the pattern enriched in light REE. These variations could not be explained easily by the simple mixing process of LREE-depleted components and LREE-enriched melt, but they imply some metamorphism process. The Rb-Sr isotopic data for Shalka are shown with the data for other several diogenites. These observations indicate that Shalka would undergo a significant extent of metamorphism followed by redistribution of REE and the disturbance of the Rb-Sr systematics. We are going to do further studies on Shalka to discuss the metamorphic process and compare it with other diogenites.

  8. Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Garbarino, John R.; Taylor, Howard E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  9. Geo-statistical analysis of Culicoides spp. distribution and abundance in Sicily, Italy.

    PubMed

    Blanda, Valeria; Blanda, Marcellocalogero; La Russa, Francesco; Scimeca, Rossella; Scimeca, Salvatore; D'Agostino, Rosalia; Auteri, Michelangelo; Torina, Alessandra

    2018-02-01

    Biting midges belonging to Culicoides imicola, Culicoides obsoletus complex and Culicoides pulicaris complex (Diptera: Ceratopogonidae) are increasingly implicated as vectors of bluetongue virus in Palaearctic regions. Culicoides obsoletus complex includes C. obsoletus (sensu stricto), C. scoticus, C. dewulfi and C. chiopterus. Culicoides pulicaris and C. lupicaris belong to the Culicoides pulicaris complex. The aim of this study was a geo-statistical analysis of the abundance and spatial distribution of Culicoides spp. involved in bluetongue virus transmission. As part of the national bluetongue surveillance plan 7081 catches were collected in 897 Sicilian farms from 2000 to 2013. Onderstepoort-type blacklight traps were used for sample collection and each catch was analysed for the presence of Culicoides spp. and for the presence and abundance of Culicoides vector species (C. imicola, C. pulicaris / C. obsoletus complexes). A geo-statistical analysis was carried out monthly via the interpolation of measured values based on the Inverse Distance Weighted method, using a GIS tool. Raster maps were reclassified into seven classes according to the presence and abundance of Culicoides, in order to obtain suitable maps for Map Algebra operations. Sicilian provinces showing a very high abundance of Culicoides vector species were Messina (80% of the whole area), Palermo (20%) and Catania (12%). A total of 5654 farms fell within the very high risk area for bluetongue (21% of the 26,676 farms active in Sicily); of these, 3483 farms were in Messina, 1567 in Palermo and 604 in Catania. Culicoides imicola was prevalent in Palermo, C. pulicaris in Messina and C. obsoletus complex was very abundant over the whole island with the highest abundance value in Messina. Our study reports the results of a geo-statistical analysis concerning the abundance and spatial distribution of Culicoides spp. in Sicily throughout the fourteen year study. It provides useful decision support in the

  10. Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Franz, H. B.; Mahaffy, P. R.; Stern, J. C.; Eigenbrode, J. L.; Steele, A.; Ming, D. W.; McAdam, A. C.; Freissinet, C.; Glavin, D. P.; Archer, P. D.; hide

    2014-01-01

    Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

  11. Abundance and Isotopic Composition of Gases in the Martian Atmosphere: First Results from the Mars Curiosity Rover

    NASA Technical Reports Server (NTRS)

    Mahaffy, Paul; Webster, Chris R.; Atreya, Sushil K.; Franz, Heather; Wong, Michael; Conrad, Pamela G.; Harpold, Dan; Jones, John J.; Leshin, Laurie, A.; Manning, Heidi; hide

    2013-01-01

    Repeated measurements of the composition of the Mars atmosphere from Curiosity Rover yield a (40)Ar/N2 ratio 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times smaller than the Viking Lander values in 1976. The unexpected change in (40)Ar/N2 ratio probably results from different instrument characteristics although we cannot yet rule out some unknown atmospheric process. The new (40)Ar/(36)Ar ratio is more aligned with Martian meteoritic values. Besides Ar and N2 the Sample Analysis at Mars instrument suite on the Curiosity Rover has measured the other principal components of the atmosphere and the isotopes. The resulting volume mixing ratios are: CO2 0.960(+/- 0.007); (40)Ar 0.0193(+/- 0.0001); N2 0.0189(+/- 0.0003); O2 1.45(+/- 0.09) x 10(exp -3); and CO 5.45(+/- 3.62) x 10(exp 4); and the isotopes (40)Ar/(36)Ar 1.9(+/- 0.3) x 10(exp 3), and delta (13)C and delta (18)O from CO2 that are both several tens of per mil more positive than the terrestrial averages. Heavy isotope enrichments support the hypothesis of large atmospheric loss. Moreover, the data are consistent with values measured in Martian meteorites, providing additional strong support for a Martian origin for these rocks.

  12. Paleobiological Implications of the Isotopic Signatures ( 13C, 15N) of Fossil Mammal Collagen in Scladina Cave (Sclayn, Belgium)

    NASA Astrophysics Data System (ADS)

    Bocherens, Hervé; Billiou, Daniel; Patou-Mathis, Marylène; Bonjean, Dominique; Otte, Marcel; Mariotti, André

    1997-11-01

    An isotopic investigation of upper Pleistocene mammal bones and teeth from Scladina cave (Sclayn, Belgium) demonstrated the very good quality of collagen preservation. A preliminary screening of the samples used the amount of nitrogen in whole bone and dentine in order to estimate the preserved amount of collagen before starting the extraction process. The isotopic abundances of fossil specimens from still-extant species are consistent with their trophic position. Moreover, the 15N isotopic abundance is higher in dentine than in bone in bears and hyenas, a phenomenon already observed in modern specimens. These results demonstrate that the isotopic compositions of samples from Scladina cave can be interpreted in ecological terms. Mammoths exhibit a high 15N isotopic abundance relative to other herbivores, as was the case in Siberian and Alaskan samples. These results suggest distinctive dietary adaptations in herbivores living in the mammoth steppe. Cave bears are clearly isotopically different from coeval brown bears, suggesting an ecological separation between species, with a pure vegetarian diet for cave bear and an omnivorous diet for brown bear.

  13. Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

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

    v, Mitroshkov; JV, Ryan

    2016-04-07

    Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types ofmore » isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.« less

  14. Long-term changes in solar wind elemental and isotopic ratios - A comparison of two lunar ilmenites of different antiquities

    NASA Technical Reports Server (NTRS)

    Becker, Richard H.; Pepin, Robert O.

    1989-01-01

    The solar wind components in two lunar ilmenites are examined. The noble gas and nitrogen elemental and isotopic abundances of lunar regolith breccia sample 79035, assumed to have been exposed to solar winds more than 2 Ga ago, are analyzed using stepwise oxidation and pyrolysis. This sample is compared with the data of Frick et al. (1988) for soil sample 71501, recently exposed to solar winds. It is observed that the two elements differ in terms of xenon abundance, helium and neon isotopic rates, and He/Ar elemental ratios. It is concluded that there have been isotopic and elemental abundance changes in solar wind composition over time.

  15. 13C metabolic flux analysis: optimal design of isotopic labeling experiments.

    PubMed

    Antoniewicz, Maciek R

    2013-12-01

    Measuring fluxes by 13C metabolic flux analysis (13C-MFA) has become a key activity in chemical and pharmaceutical biotechnology. Optimal design of isotopic labeling experiments is of central importance to 13C-MFA as it determines the precision with which fluxes can be estimated. Traditional methods for selecting isotopic tracers and labeling measurements did not fully utilize the power of 13C-MFA. Recently, new approaches were developed for optimal design of isotopic labeling experiments based on parallel labeling experiments and algorithms for rational selection of tracers. In addition, advanced isotopic labeling measurements were developed based on tandem mass spectrometry. Combined, these approaches can dramatically improve the quality of 13C-MFA results with important applications in metabolic engineering and biotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

    2015-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model

  17. 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.

  18. Comparison of normalization methods for the analysis of metagenomic gene abundance data.

    PubMed

    Pereira, Mariana Buongermino; Wallroth, Mikael; Jonsson, Viktor; Kristiansson, Erik

    2018-04-20

    In shotgun metagenomics, microbial communities are studied through direct sequencing of DNA without any prior cultivation. By comparing gene abundances estimated from the generated sequencing reads, functional differences between the communities can be identified. However, gene abundance data is affected by high levels of systematic variability, which can greatly reduce the statistical power and introduce false positives. Normalization, which is the process where systematic variability is identified and removed, is therefore a vital part of the data analysis. A wide range of normalization methods for high-dimensional count data has been proposed but their performance on the analysis of shotgun metagenomic data has not been evaluated. Here, we present a systematic evaluation of nine normalization methods for gene abundance data. The methods were evaluated through resampling of three comprehensive datasets, creating a realistic setting that preserved the unique characteristics of metagenomic data. Performance was measured in terms of the methods ability to identify differentially abundant genes (DAGs), correctly calculate unbiased p-values and control the false discovery rate (FDR). Our results showed that the choice of normalization method has a large impact on the end results. When the DAGs were asymmetrically present between the experimental conditions, many normalization methods had a reduced true positive rate (TPR) and a high false positive rate (FPR). The methods trimmed mean of M-values (TMM) and relative log expression (RLE) had the overall highest performance and are therefore recommended for the analysis of gene abundance data. For larger sample sizes, CSS also showed satisfactory performance. This study emphasizes the importance of selecting a suitable normalization methods in the analysis of data from shotgun metagenomics. Our results also demonstrate that improper methods may result in unacceptably high levels of false positives, which in turn may lead

  19. Perchlorate in the Great Lakes: isotopic composition and origin.

    PubMed

    Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

    2014-10-07

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

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

    PubMed

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

    1999-07-01

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

  1. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  2. Stable Isotope Quantitative N-Glycan Analysis by Liquid Separation Techniques and Mass Spectrometry.

    PubMed

    Mittermayr, Stefan; Albrecht, Simone; Váradi, Csaba; Millán-Martín, Silvia; Bones, Jonathan

    2017-01-01

    Liquid phase separation analysis and subsequent quantitation remains a challenging task for protein-derived oligosaccharides due to their inherent structural complexity and diversity. Incomplete resolution or co-detection of multiple glycan species complicates peak area-based quantitation and associated statistical analysis when optical detection methods are used. The approach outlined herein describes the utilization of stable isotope variants of commonly used fluorescent tags that allow for mass-based glycan identification and relative quantitation following separation by liquid chromatography (LC) or capillary electrophoresis (CE). Comparability assessment of glycoprotein-derived oligosaccharides is performed by derivatization with commercially available isotope variants of 2-aminobenzoic acid or aniline and analysis by LC- and CE-mass spectrometry. Quantitative information is attained from the extracted ion chromatogram/electropherogram ratios generated from the light and heavy isotope clusters.

  3. 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.

  4. Aerosol carbon isotope composition over Baltic Sea

    NASA Astrophysics Data System (ADS)

    Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

    2017-04-01

    Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

  5. Inter- and intraindividual correlations of background abundances of (2)H, (18)O and (17)O in human urine and implications for DLW measurements.

    PubMed

    Berman, E S F; Melanson, E L; Swibas, T; Snaith, S P; Speakman, J R

    2015-10-01

    The method of choice for measuring total energy expenditure in free-living individuals is the doubly labeled water (DLW) method. This experiment examined the behavior of natural background isotope abundance fluctuations within and between individuals over time to assess possible methods of accounting for variations in the background isotope abundances to potentially improve the precision of the DLW measurement. In this work, we measured natural background variations in (2)H, (18)O and (17)O in water from urine samples collected from 40 human subjects who resided in the same geographical area. Each subject provided a urine sample for 30 consecutive days. Isotopic abundances in the samples were measured using Off-Axis Integrated Cavity Output Spectroscopy. Autocorrelation analyses demonstrated that the background isotopes in a given individual were not temporally correlated over the time scales of typical DLW studies. Using samples obtained from different individuals on the same calendar day, cross-correlation analyses demonstrated that the background variations of different individuals were not correlated in time. However, the measured ratios of the three isotopes (2)H, (18)O and (17)O were highly correlated (R(2)=0.89-0.96). Although neither specific timing of DLW water studies nor intraindividual comparisons were found to be avenues for reducing the impact of background isotope abundance fluctuations on DLW studies, strong inter-isotope correlations within an individual confirm that use of a dosing ratio of 8‰:1‰ (0.6 p.p.m.: p.p.m.) optimizes DLW precision. Theoretical implications for the possible use of (17)O measurements within a DLW study require further study.

  6. Hyperfine Structure and Abundances of Heavy Elements in 68 Tauri (HD 27962)

    NASA Astrophysics Data System (ADS)

    Martinet, S.; Monier, R.

    2017-12-01

    HD 27962, also known as 68 Tauri, is a Chemically Peculiar Am star member of the Hyades Open Cluster in the local arm of the Galaxy. We have modeled the high resolution SOPHIE (R=75000) spectrum of 68 Tauri using updated model atmosphere and spectrum synthesis to derive chemical abundances in its atmosphere. In particular, we have studied the effect of the inclusion of Hyperfine Structure of various Baryum isotopes on the determination of the Baryum abundance in 68 Tauri. We have also derived new abundances using updated accurate atomic parameters retrieved from the NIST database.

  7. A Differential Abundance Analysis of Very Metal-poor Stars

    NASA Astrophysics Data System (ADS)

    O'Malley, Erin M.; McWilliam, Andrew; Chaboyer, Brian; Thompson, Ian

    2017-04-01

    We have performed a differential line-by-line chemical abundance analysis, ultimately relative to the Sun, of nine very metal-poor main-sequence (MS) halo stars, near [Fe/H] = -2 dex. Our abundances range from -2.66≤slant [{Fe}/{{H}}]≤slant -1.40 dex with conservative uncertainties of 0.07 dex. We find an average [α/Fe] = 0.34 ± 0.09 dex, typical of the Milky Way. While our spectroscopic atmosphere parameters provide good agreement with Hubble Space Telescope parallaxes, there is significant disagreement with temperature and gravity parameters indicated by observed colors and theoretical isochrones. Although a systematic underestimate of the stellar temperature by a few hundred degrees could explain this difference, it is not supported by current effective temperature studies and would create large uncertainties in the abundance determinations. Both 1D and < 3{{D}}> hydrodynamical models combined with separate 1D non-LTE effects do not yet account for the atmospheres of real metal-poor MS stars, but a fully 3D non-LTE treatment may be able to explain the ionization imbalance found in this work.

  8. web-based interactive data processing: application to stable isotope metrology.

    PubMed

    Verkouteren, R M; Lee, J N

    2001-08-01

    To address a fundamental need in stable isotope metrology, the National Institute of Standards and Technology (NIST) has established a web-based interactive data-processing system accessible through a common gateway interface (CGI) program on the internet site http://www. nist.gov/widps-co2. This is the first application of a web-based tool that improves the measurement traceability afforded by a series of NIST standard materials. Specifically, this tool promotes the proper usage of isotope reference materials (RMs) and improves the quality of reported data from extensive measurement networks. Through the International Atomic Energy Agency (IAEA), we have defined standard procedures for stable isotope measurement and data-processing, and have determined and applied consistent reference values for selected NIST and IAEA isotope RMs. Measurement data of samples and RMs are entered into specified fields on the web-based form. These data are submitted through the CGI program on a NIST Web server, where appropriate calculations are performed and results returned to the client. Several international laboratories have independently verified the accuracy of the procedures and algorithm for measurements of naturally occurring carbon-13 and oxygen-18 abundances and slightly enriched compositions up to approximately 150% relative to natural abundances. To conserve the use of the NIST RMs, users may determine value assignments for a secondary standard to be used in routine analysis. Users may also wish to validate proprietary algorithms embedded in their laboratory instrumentation, or specify the values of fundamental variables that are usually fixed in reduction algorithms to see the effect on the calculations. The results returned from the web-based tool are limited in quality only by the measurements themselves, and further value may be realized through the normalization function. When combined with stringent measurement protocols, two- to threefold improvements have been

  9. Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.

    PubMed

    Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L

    2014-11-01

    This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. An elemental abundance analysis of the superficially normal A star Vega

    NASA Technical Reports Server (NTRS)

    Adelman, Saul J.; Gulliver, Austin F.

    1990-01-01

    An elemental abundance analysis of Vega has been performed using high-signal-to-noise 2.4 A/mm Reticon observations of the region 4313-4809 A. Vega is found to be a metal-poor star with a mean underabundance of 0.60 dex. The He/H ratio of 0.03 as derived from He I 4472 A suggests that the superficial helium convection zone has disappeared and that radiative diffusion is producing the photospheric abundance anomalies.

  11. Hydrology of Bishop Creek, California: An Isotopic Analysis

    Treesearch

    Michael L. Space; John W. Hess; Stanley D. Smith

    1989-01-01

    Five power generation plants along an eleven kilometer stretch divert Bishop Creek water for hydro-electric power. Stream diversion may be adversely affecting the riparian vegetation. Stable isotopic analysis is employed to determine surface water/ground-water interactions along the creek. surface water originates primarily from three headwater lakes. Discharge into...

  12. Recent developments in application of stable isotope analysis on agro-product authenticity and traceability.

    PubMed

    Zhao, Yan; Zhang, Bin; Chen, Gang; Chen, Ailiang; Yang, Shuming; Ye, Zhihua

    2014-02-15

    With the globalisation of agro-product markets and convenient transportation of food across countries and continents, the potential for distribution of mis-labelled products increases accordingly, highlighting the need for measures to identify the origin of food. High quality food with identified geographic origin is a concern not only for consumers, but also for agriculture farmers, retailers and administrative authorities. Currently, stable isotope ratio analysis in combination with other chemical methods gradually becomes a promising approach for agro-product authenticity and traceability. In the last five years, a growing number of research papers have been published on tracing agro-products by stable isotope ratio analysis and techniques combining with other instruments. In these reports, the global variety of stable isotope compositions has been investigated, including light elements such as C, N, H, O and S, and heavy isotopes variation such as Sr and B. Several factors also have been considered, including the latitude, altitude, evaporation and climate conditions. In the present paper, an overview is provided on the authenticity and traceability of the agro-products from both animal and plant sources by stable isotope ratio analysis. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. New approaches to the Moon's isotopic crisis

    PubMed Central

    Melosh, H. J.

    2014-01-01

    Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth–Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. PMID:25114301

  14. Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

    PubMed

    Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

    2016-05-01

    Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

  15. Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

    PubMed

    Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

    2017-02-15

    High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of 29 Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O 2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO + and SiO 2 + ion species was performed, and we found that SiO + ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO 3 ). For SiO 2 + , no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. 28 Si 16 O 18 O + , 30 Si 16 O 16 O + ). The developed method was validated by measuring a series of reference solutions with different 29 Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0

  16. 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.

  17. Isotopes as Tracers of the Hawaiian Coffee-Producing Regions

    PubMed Central

    2011-01-01

    Green coffee bean isotopes have been used to trace the effects of different climatic and geological characteristics associated with the Hawaii islands. Isotope ratio mass spectrometry (IRMS) and inductively coupled plasma mass spectrometry ((MC)-ICP-SFMS and ICP-QMS) were applied to determine the isotopic composition of carbon (δ13C), nitrogen (δ15N), sulfur (δ34S), and oxygen (δ18O), the isotope abundance of strontium (87Sr/86Sr), and the concentrations of 30 different elements in 47 green coffees. The coffees were produced in five Hawaii regions: Hawaii, Kauai, Maui, Molokai, and Oahu. Results indicate that coffee plant seed isotopes reflect interactions between the coffee plant and the local environment. Accordingly, the obtained analytical fingerprinting could be used to discriminate between the different Hawaii regions studied. PMID:21838232

  18. Compound specific isotope analysis to investigate pesticide degradation in lysimeter experiments at field conditions

    NASA Astrophysics Data System (ADS)

    Ryabenko, Evgenia; Elsner, Martin; Bakkour, Rani; Hofstetter, Thomas; Torrento, Clara; Hunkeler, Daniel

    2015-04-01

    The frequent detection of organic micropollutants such as pesticides, consumer care products or pharmaceuticals in water is an increasing concern for human and ecosystem health. Degradation analysis of these compounds can be challenging in complex systems due to the fact that metabolites are not always found and mass balances frequently cannot be closed. Many abiotic and biotic degradation pathways cause, however, distinct isotope fractionation, where light isotopes are transferred preferentially from the reactant to the product pool (normal isotope fractionation). Compound-specific isotope analysis (CSIA) of multiple elements is a particularly powerful method to evaluate organic micropollutant transformation, because it can even give pathway-specific isotope fractionation (1,2). Available CSIA field studies, however, have focused almost exclusively on volatile petroleum and chlorinated hydrocarbons, which are present in high concentrations in the environment and can be extracted easily from water for GC-IRMS analysis. In the case of micropollutants, such as pesticides, CSIA in more challenging since it needs to be conducted at lower concentrations and requires pre-concentration, purification and high chromatographic performance (3). In this study we used lysimeters experiments to analyze transformation of atrazine, acetochlor, metolachlor and chloridazone by studying associated isotope fractionation. The project combines a) analytical method development for CSIA, b) identification of pathways of micropollutant degradation and c) quantification of transformation processes under field condition. The pesticides were applied both, at the soil surface and below the top soil under field-relevant concentrations in May 2014. After typical irrigation of the lysimeters, seepage water was collected in 50L bottles and stored for further SPE and CSIA. Here we present the very first result of a) analytical method development, b) improvement of SPE methods for complex pesticide

  19. Abundance analysis of roAp stars. IV. HD24712

    NASA Astrophysics Data System (ADS)

    Ryabchikova, T. A.; Landstreet, J. D.; Gelbmann, M. J.; Bolgova, G. T.; Tsymbal, V. V.; Weiss, W. W.

    1997-11-01

    We present the first abundance analysis of the rapidly oscillating chemically peculiar star HD24712, and determine a T_eff,=7250K, log {g},=4.3, and xi_t ,=1kms(-1) . Microturbulence seems to be entirely simulated by a magnetic field with a polar field strength of 4.4kG and of dipolar structure, both of which are supported by our polarimetric observations. Rotation of HD24712 and a spotty surface distribution of the elements result in different mean abundances for different (magnetic) phases. Our results do not support the hypothesis of a monotonic correlation between the amplitude of abundance variations and the atomic number Z, and we present arguments in favour of one of the rotation periods (Prot=12\\fd 4610) discussed in the literature. Rare earth elements are the most overabundant elements relative to the sun, and they have the largest abundance amplitude during a rotation cycle; only Mg has a larger amplitude. For HD24712 we find a clear overabundance of Co while most of the other iron peak elements are underabundant. A comparison of the abundance pattern with the other three roAp stars analyzed so far by us concludes the paper. A systematic difference between surface gravities obtained from spectroscopy and from both asteroseismology and evolutionary tracks is found for the roAp stars HD 24712, alpha Cir, and gamma Equ. Based on observations obtained with the Canada-France-Hawaii telescope, operated by the National Research Council of Canada, the Centre Centre National de la Recherche Scientifique de France, and the University of Hawaii, and on observations obtained at CARSO, Las Campanas, Chile

  20. Evaluating methane inventories by isotopic analysis in the London region.

    PubMed

    Zazzeri, G; Lowry, D; Fisher, R E; France, J L; Lanoisellé, M; Grimmond, C S B; Nisbet, E G

    2017-07-07

    A thorough understanding of methane sources is necessary to accomplish methane reduction targets. Urban environments, where a large variety of methane sources coexist, are one of the most complex areas to investigate. Methane sources are characterised by specific δ 13 C-CH 4 signatures, so high precision stable isotope analysis of atmospheric methane can be used to give a better understanding of urban sources and their partition in a source mix. Diurnal measurements of methane and carbon dioxide mole fraction, and isotopic values at King's College London, enabled assessment of the isotopic signal of the source mix in central London. Surveys with a mobile measurement system in the London region were also carried out for detection of methane plumes at near ground level, in order to evaluate the spatial allocation of sources suggested by the inventories. The measured isotopic signal in central London (-45.7 ±0.5‰) was more than 2‰ higher than the isotopic value calculated using emission inventories and updated δ 13 C-CH 4 signatures. Besides, during the mobile surveys, many gas leaks were identified that are not included in the inventories. This suggests that a revision of the source distribution given by the emission inventories is needed.

  1. 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.

  2. Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

    PubMed Central

    Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

    2014-01-01

    Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

  3. VizieR Online Data Catalog: C and O isotopic ratios in Arcturus and Aldebaran (Abia+ 2012)

    NASA Astrophysics Data System (ADS)

    Abia, C.; Palmerini, S.; Busso, M.; Cristallo, S.

    2012-10-01

    CNO abundances, C and O isotopic ratios and equivalent diffusive coefficients (D) are given for the calculated extra-mixing models. For Arcturus we used the electronic version of the Infrared Atlas Spectrum by Hinkle et al. (1995, Cat. J/PASP/107/1042; resolution 0.01cm-1), and for Aldebaran we used a spectrum obtained on February 6, 1980 at the KPNO 4m Coude telescope using a Fourier transform spectrometer, kindly provided by K. Hinkle (resolution 0.016cm-1) The first 2 rows of table4 report the CNO abundances and isotopic ratios resulting from the observations. The other rows give the CNO abundances and isotopic ratios accounted for by the FDU in the three stellar models considered of 1.3Mo, 1.2Mo and 1.08Mo (see the paper for more details). (1 data file).

  4. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate

    PubMed Central

    Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

    2014-01-01

    The dynamics of nitrate (NO−3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO−3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO−3-use mechanisms. The concentration and natural isotopes of tissue NO−3 can offer insights into the plant NO−3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO−3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO−3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO−3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO−3 in plants, and discuss the implications of NO−3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO−3 and plant ecophysiological functions in interspecific and intra-plant NO−3 variations. We introduce N and O isotope systematics of NO−3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ18O and Δ17O); and isotope mass-balance calculations to constrain sources and reduction of NO−3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ18O-NO−3 variation, and summarize the uncertainties in using tissue NO−3 parameters to interpret plant NO−3 utilization

  6. Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate.

    PubMed

    Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

    2014-01-01

    The dynamics of nitrate (NO(-) 3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO(-) 3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO(-) 3-use mechanisms. The concentration and natural isotopes of tissue NO(-) 3 can offer insights into the plant NO(-) 3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO(-) 3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO(-) 3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO(-) 3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO(-) 3 in plants, and discuss the implications of NO(-) 3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO(-) 3 and plant ecophysiological functions in interspecific and intra-plant NO(-) 3 variations. We introduce N and O isotope systematics of NO(-) 3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ(18)O and Δ(17)O); and isotope mass-balance calculations to constrain sources and reduction of NO(-) 3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ(18)O-NO(-) 3 variation, and summarize the uncertainties in using tissue NO(-) 3 parameters to interpret

  7. The isotopic composition of cosmic ray calcium

    NASA Technical Reports Server (NTRS)

    Krombel, K. E.; Wiedenbeck, M. E.

    1985-01-01

    Data from the high energy cosmic ray experiment on the international sun earth explorer 3 (ISEE-3) spacecraft have been used to study the isotopic composition of cosmic ray calcium at an energy of approx. 260 MeV/amu. The arriving calcium is found to consist of (32 + or - 6)%. A propagation model consistent with both the light and the subiron secondary element abundances was used for the interpretation of the observed calcium composition. The measured 42Ca+43Ca+44Ca abundance is consistent with the calculated secondary production, while the 40Ca abundance implies a source ratio of 40Ca/Fe = (7.0 + or - 1.7)%.

  8. [Humus composition and stable carbon isotope natural abundance in paddy soil under long-term fertilization].

    PubMed

    Ma, Li; Yang, Lin-Zhang; Ci, En; Wang, Yan; Yin, Shi-Xue; Shen, Ming-Xing

    2008-09-01

    Soil samples were collected from an experimental paddy field with long-term (26 years) fertilization in Taihu Lake region of Jiangsu Province to study the effects of different fertilization on the organic carbon distribution and stable carbon isotope natural abundance (delta 13C) in the soil profile, and on the humus composition. The results showed that long-term fertilization increased the organic carbon content in top soil significantly, and there was a significantly negative exponential correlation between soil organic carbon content and soil depth (P < 0.01). The organic carbon content in 10-30 cm soil layer under chemical fertilizations and in 20-40 cm soil layer under organic fertilizations was relatively stable. Soil delta 13C increased gradually with soil depth, its variation range being from -24% per thousand to -28 per thousand, and had a significantly negative linear correlation with soil organic carbon content (P < 0.05). In 0-20 cm soil layer, the delta 13C in treatments organic manure (M), M + NP, M + NPK, M + straw (R) + N, and R + N decreased significantly; while in 30-50 cm soil layer, the delta 13C in all organic fertilization treatments except R + N increased significantly. Tightly combined humus (humin) was the main humus composition in the soil, occupying 50% or more, and the rest were loosely and stably combined humus. Long-term fertilization increased the content of loosely combined humus and the ratio of humic acid (HA) to fulvic acid (FA).

  9. An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, T.B.

    2001-01-01

    An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2H/1H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H3+ contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: -630??? to -790??? for the second gas and -368??? to -462??? for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the ?? values so that the gases with the lowest and highest 2H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85???. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate. ?? Springer-Verlag 2001.

  10. Uranium Isotopic Ratio Measurements of U3O8 Reference Materials by Atom Probe Tomography

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

    Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG

    2016-01-01

    We report results of measurements of isotopic ratios obtained with atom probe tomography on U3O8 reference materials certified for their isotopic abundances of uranium. The results show good agreement with the certified values. High backgrounds due to tails from adjacent peaks complicate the measurement of the integrated peak areas as well as the fact that only oxides of uranium appear in the spectrum, the most intense of which is doubly charged. In addition, lack of knowledge of other instrumental parameters, such as the dead time, may bias the results. Isotopic ratio measurements can be performed at the nanometer-scale with themore » expectation of sensible results. The abundance sensitivity and mass resolving power of the mass spectrometer are not sufficient to compete with magnetic-sector instruments but are not far from measurements made by ToF-SIMS of other isotopic systems. The agreement of the major isotope ratios is more than sufficient to distinguish most anthropogenic compositions from natural.« less

  11. Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

    NASA Astrophysics Data System (ADS)

    Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

    2013-04-01

    samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

  12. Cr Isotopes in Allende Ca-Al-rich Inclusions

    NASA Technical Reports Server (NTRS)

    Bogdanovski, O.; Papanastassiou, D. A.; Wasserburg, G. J.

    2002-01-01

    We have determined Cr isotope compositions in minerals from Allende CAI in order to address the initial 53Mn (half-life 3.7 Ma) abundance in the solar system. Additional information is contained in the original extended abstract.

  13. Quinone-based stable isotope probing for assessment of 13C substrate-utilizing bacteria

    NASA Astrophysics Data System (ADS)

    Kunihiro, Tadao; Katayama, Arata; Demachi, Toyoko; Veuger, Bart; Boschker, Henricus T. S.; van Oevelen, Dick

    2015-04-01

    In this study, we attempted to establish quinone-stable-isotope probing (SIP) technique to link substrate-utilizing bacterial group to chemotaxonomic group in bacterial community. To identify metabolically active bacterial group in various environments, SIP techniques combined with biomarkers have been widely utilized as an attractive method for environmental study. Quantitative approaches of the SIP technique have unique advantage to assess substrate-incorporation into bacteria. As a most major quantitative approach, SIP technique based on phospholipid-derived fatty acids (PLFA) have been applied to simultaneously assess substrate-incorporation rate into bacteria and microbial community structure. This approach is powerful to estimate the incorporation rate because of the high sensitivity due to the detection by a gas chromatograph-combustion interface-isotope ratio mass spectrometer (GC-c-IRMS). However, its phylogenetic resolution is limited by specificity of a compound-specific marker. We focused on respiratory quinone as a biomarker. Our previous study found a good correlation between concentrations of bacteria-specific PLFAs and quinones over several orders of magnitude in various marine sediments, and the quinone method has a higher resolution (bacterial phylum level) for resolving differences in bacterial community composition more than that of bacterial PLFA. Therefore, respiratory quinones are potentially good biomarkers for quantitative approaches of the SIP technique. The LC-APCI-MS method as molecular-mass based detection method for quinone was developed and provides useful structural information for identifying quinone molecular species in environmental samples. LC-MS/MS on hybrid triple quadrupole/linear ion trap, which enables to simultaneously identify and quantify compounds in a single analysis, can detect high molecular compounds with their isotope ions. Use of LC-MS/MS allows us to develop quinone-SIP based on molecular mass differences due to

  14. Accurate abundance determinations in S stars

    NASA Astrophysics Data System (ADS)

    Neyskens, P.; Van Eck, S.; Plez, B.; Goriely, S.; Siess, L.; Jorissen, A.

    2011-12-01

    S-type stars are thought to be the first objects, during their evolution on the asymptotic giant branch (AGB), to experience s-process nucleosynthesis and third dredge-ups, and therefore to exhibit s-process signatures in their atmospheres. Until present, the modeling of these processes is subject to large uncertainties. Precise abundance determinations in S stars are of extreme importance for constraining e.g., the depth and the formation of the 13C pocket. In this paper a large grid of MARCS model atmospheres for S stars is used to derive precise abundances of key s-process elements and iron. A first estimation of the atmospheric parameters is obtained using a set of well-chosen photometric and spectroscopic indices for selecting the best model atmosphere of each S star. Abundances are derived from spectral line synthesis, using the selected model atmosphere. Special interest is paid to technetium, an element without stable isotopes. Its detection in stars is considered as the best possible signature that the star effectively populates the thermally-pulsing AGB (TP-AGB) phase of evolution. The derived Tc/Zr abundances are compared, as a function of the derived [Zr/Fe] overabundances, with AGB stellar model predictions. The computed [Zr/Fe] overabundances are in good agreement with the AGB stellar evolution model predictions, while the Tc/Zr abundances are slightly over-predicted. This discrepancy can help to set stronger constraints on nucleosynthesis and mixing mechanisms in AGB stars.

  15. Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

    PubMed Central

    Weisler, M I; Woodhead, J D

    1995-01-01

    The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

  16. Characterization of phenol and cresol biodegradation by compound-specific stable isotope analysis.

    PubMed

    Wei, Xi; Gilevska, Tetyana; Wetzig, Felix; Dorer, Conrad; Richnow, Hans-Hermann; Vogt, Carsten

    2016-03-01

    Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Growth history of cultured pearl oysters based on stable oxygen isotope analysis

    NASA Astrophysics Data System (ADS)

    Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

    2007-12-01

    We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

  18. Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

    NASA Astrophysics Data System (ADS)

    Herzka, Sharon Z.

    2005-07-01

    Assessing connectivity is fundamental to understanding the population dynamics of fishes. I propose that isotopic analyses can greatly contribute to studies of connectivity in estuarine fishes due to the high diversity of isotopic signatures found among estuarine habitats and the fact that variations in isotopic composition at the base of a food web are reflected in the tissues of consumers. Isotopic analysis can be used for identifying nursery habitats and estimating their contribution to adult populations. If movement to a new habitat is accompanied by a shift to foods of distinct isotopic composition, recent immigrants and residents can be distinguished based on their isotopic ratios. Movement patterns thus can be reconstructed based on information obtained from individuals. A key consideration is the rate of isotopic turnover, which determines the length of time that an immigrant to a given habitat will be distinguishable from a longtime resident. A literature survey indicated that few studies have measured turnover rates in fishes and that these have focused on larvae and juveniles. These studies reveal that biomass gain is the primary process driving turnover rates, while metabolic turnover is either minimal or undetectable. Using a simple dilution model and biomass-specific growth rates, I estimated that young fishes with fast growth rates will reflect the isotopic composition of a new diet within days or weeks. Older or slower-growing individuals may take years or never fully equilibrate. Future studies should evaluate the factors that influence turnover rates in fishes during various stages of the life cycle and in different tissues, as well as explore the potential for combining stable isotope and otolith microstructure analyses to examine the relationship between demographic parameters, movement and connectivity.

  19. 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

  20. Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

  1. Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

    2016-06-01

    We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

  2. Mid-IR enhanced laser ablation molecular isotopic spectrometry

    NASA Astrophysics Data System (ADS)

    Brown, Staci; Ford, Alan; Akpovo, Codjo A.; Johnson, Lewis

    2016-08-01

    A double-pulsed laser-induced breakdown spectroscopy (DP-LIBS) technique utilizing wavelengths in the mid-infrared (MIR) for the second pulse, referred to as double-pulse LAMIS (DP-LAMIS), was examined for its effect on detection limits compared to single-pulse laser ablation molecular isotopic spectrometry (LAMIS). A MIR carbon dioxide (CO2) laser pulse at 10.6 μm was employed to enhance spectral emissions from nanosecond-laser-induced plasma via mid-IR reheating and in turn, improve the determination of the relative abundance of isotopes in a sample. This technique was demonstrated on a collection of 10BO and 11BO molecular spectra created from enriched boric acid (H3BO3) isotopologues in varying concentrations. Effects on the overall ability of both LAMIS and DP-LAMIS to detect the relative abundance of boron isotopes in a starting sample were considered. Least-squares fitting to theoretical models was used to deduce plasma parameters and understand reproducibility of results. Furthermore, some optimization for conditions of the enhanced emission was achieved, along with a comparison of the overall emission intensity, plasma density, and plasma temperature generated by the two techniques.

  3. Precise Analysis of Gallium Isotopic Composition by MC-ICP-MS.

    PubMed

    Yuan, Wei; Chen, Jiu Bin; Birck, Jean-Louis; Yin, Zuo Ying; Yuan, Sheng Liu; Cai, Hong Ming; Wang, Zhong Wei; Huang, Qiang; Wang, Zhu Hong

    2016-10-04

    Though an isotope approach could be beneficial for better understanding the biogeochemical cycle of gallium (Ga), an analogue of the monoisotopic element aluminum (Al), the geochemistry of Ga isotopes has not been widely elaborated. We developed a two-step method for purifying Ga from geological (biological) samples for precise measurement of Ga isotope ratio using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Ga was thoroughly separated from other matrix elements using two chromatographic columns loaded with AG 1-X4 and Ln-spec resin, respectively. The separation method was carefully calibrated using both synthetic and natural samples and validated by assessing the extraction yield (99.8 ± 0.8%, 2SD, n = 23) and the reproducibility (2SD uncertainty better than 0.05‰, n = 116) of the measured isotopic ratio (expressed as δ 71 Ga). The validation of the whole protocol, together with instrumental analysis, was confirmed by the investigation of the matrix effect, the result of a standard addition experiment, and the comparison of Ga isotope measurement on two mass spectrometers-Nu Plasma II and Neptune Plus. Although the measurements using the sample-standard bracketing (SSB) correction method on both instruments resulted in identical δ 71 Ga values for reference materials, the modified empirical external normalization (MEEN) method gave relatively better precision compared to SSB on Neptune. Our preliminary results showed large variation of δ 71 Ga (up to 1.83‰) for 10 standards, with higher values in industrially produced materials, implying potential application of Ga isotopes.

  4. Martian carbon dioxide: Clues from isotopes in SNC meteorites

    NASA Technical Reports Server (NTRS)

    Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.

    1993-01-01

    Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

  5. Models of earth structure inferred from neodymium and strontium isotopic abundances

    PubMed Central

    Wasserburg, G. J.; DePaolo, D. J.

    1979-01-01

    A simplified model of earth structure based on the Nd and Sr isotopic characteristics of oceanic and continental tholeiitic flood basalts is presented, taking into account the motion of crustal plates and a chemical balance for trace elements. The resulting structure that is inferred consists of a lower mantle that is still essentially undifferentiated, overlain by an upper mantle that is the residue of the original source from which the continents were derived. PMID:16592688

  6. Long-term variations of fluxes of solar protons and helium isotopes

    NASA Astrophysics Data System (ADS)

    Anufriev, G. S.

    2012-11-01

    The fluxes of hydrogen and helium isotopes in the solar wind are reconstructed over a long time scale since the present time up to 600 million years back. Abundances of helium isotopes, obtained in the helium isotopic analysis made for 8 lunar soil samples, were used as initial data in the reconstruction procedure. Samples were taken off from various levels of the 1.6-m core of lunar soil delivered by the automatic Luna-24 station in 1976. The data on modern hydrogen and helium fluxes were used as well. The developed reconstruction procedure allowed one to select various solar wind components in a "gross" composition. Proton flux variations over the interval of 600 million years do not exceed a value of 40 %. Helium flux variations reach a value of 1.5-2 relative to the average value. Most likely, this circumstance is caused by considerable variations of a number of coronal mass ejections ( CME) enriched by helium. The arguments in favor of solar activity polycyclicity on a long time scale are discussed.

  7. Calcium Isotope Analysis with "Peak Cut" Method on Column Chemistry

    NASA Astrophysics Data System (ADS)

    Zhu, H.; Zhang, Z.; Liu, F.; Li, X.

    2017-12-01

    To eliminate isobaric interferences from elemental and molecular isobars (e.g., 40K+, 48Ti+, 88Sr2+, 24Mg16O+, 27Al16O+) on Ca isotopes during mass determination, samples should be purified through ion-exchange column chemistry before analysis. However, large Ca isotopic fractionation has been observed during column chemistry (Russell and Papanastassiou, 1978; Zhu et al., 2016). Therefore, full recovery during column chemistry is greatly needed, otherwise uncertainties would be caused by poor recovery (Zhu et al., 2016). Generally, matrix effects could be enhanced by full recovery, as other elements might overlap with Ca cut during column chemistry. Matrix effects and full recovery are difficult to balance and both need to be considered for high-precision analysis of stable Ca isotopes. Here, we investigate the influence of poor recovery on δ44/40Ca using TIMS with the double spike technique. The δ44/40Ca values of IAPSO seawater, ML3B-G and BHVO-2 in different Ca subcats (e.g., 0-20, 20-40, 40-60, 60-80, 80-100%) with 20% Ca recovery on column chemistry display limited variation after correction by the 42Ca-43Ca double spike technique with the exponential law. Notably, δ44/40Ca of each Ca subcut is quite consistent with δ44/40Ca of Ca cut with full recovery within error. Our results indicate that the 42Ca-43Ca double spike technique can simultaneously correct both of the Ca isotopic fractionation that occurred during column chemistry and thermal ionization mass spectrometry (TIMS) determination properly, because both of the isotopic fractionation occurred during analysis follow the exponential law well. Therefore, we propose the "peak cut" method on Ca column chemistry for samples with complex matrix effects. Briefly, for samples with low Ca contents, we can add the double spike before column chemistry, and only collect the middle of the Ca eluate and abandon the both sides of Ca eluate that might overlap with other elements (e.g., K, Sr). This method would

  8. Evaluating gull diets: A comparison of conventional methods and stable isotope analysis

    USGS Publications Warehouse

    Weiser, Emily L.; Powell, Abby N.

    2011-01-01

    Samples such as regurgitated pellets and food remains have traditionally been used in studies of bird diets, but these can produce biased estimates depending on the digestibility of different foods. Stable isotope analysis has been developed as a method for assessing bird diets that is not biased by digestibility. These two methods may provide complementary or conflicting information on diets of birds, but are rarely compared directly. We analyzed carbon and nitrogen stable isotope ratios of feathers of Glaucous Gull (Larus hyperboreus) chicks from eight breeding colonies in northern Alaska, and used a Bayesian mixing model to generate a probability distribution for the contribution of each food group to diets. We compared these model results with probability distributions from conventional diet samples (pellets and food remains) from the same colonies and time periods. Relative to the stable isotope estimates, conventional analysis often overestimated the contributions of birds and small mammals to gull diets and often underestimated the contributions of fish and zooplankton. Both methods gave similar estimates for the contributions of scavenged caribou, miscellaneous marine foods, and garbage to diets. Pellets and food remains therefore may be useful for assessing the importance of garbage relative to certain other foods in diets of gulls and similar birds, but are clearly inappropriate for estimating the potential impact of gulls on birds, small mammals, or fish. However, conventional samples provide more species-level information than stable isotope analysis, so a combined approach would be most useful for diet analysis and assessing a predator's impact on particular prey groups.

  9. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    NASA Astrophysics Data System (ADS)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  10. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  11. Thermal effects on rare earth element and strontium isotope chemistry in single conodont elements

    NASA Astrophysics Data System (ADS)

    Armstrong, H. A.; Pearson, D. G.; Griselin, M.

    2001-02-01

    A low-blank, high sensitivity isotope dilution, ICP-MS analytical technique has been used to obtain REE abundance data from single conodont elements weighing as little as 5 μg. Sr isotopes can also be measured from the column eluants enabling Sr isotope ratios and REE abundance to be determined from the same dissolution. Results are comparable to published analyses comprising tens to hundreds of elements. To study the effects of thermal metamorphism on REE and strontium mobility in conodonts, samples were selected from a single bed adjacent to a basaltic dyke and from the internationally used colour alteration index (CAI) "standard set." Our analyses span the range of CAI 1 to 8. Homogeneous REE patterns, "bell-shaped" shale-normalised REE patterns are observed across the range of CAI 1 to 6 in both sample sets. This pattern is interpreted as the result of adsorption during early diagenesis and could reflect original seawater chemistry. Above CAI 6 REE patterns become less predictable and perturbations from the typical REE pattern are likely to be due to the onset of apatite recrystallisation. Samples outside the contact aureole of the dyke have a mean 87Sr/ 86Sr ratio of 0.708165, within the broad range of published mid-Carboniferous seawater values. Our analysis indicates conodonts up to CAI 6 record primary geochemical signals that may be a proxy for ancient seawater.

  12. Sr-Nd-Hf Isotopic Analysis of <10 mg Dust Samples: Implications for Ice Core Dust Source Fingerprinting

    NASA Astrophysics Data System (ADS)

    Újvári, Gábor; Wegner, Wencke; Klötzli, Urs; Horschinegg, Monika; Hippler, Dorothee

    2018-01-01

    Combined Sr-Nd-Hf isotopic data of two reference materials (AGV-1/BCR2) and 50, 10, and 5 mg aliquots of carbonate-free fine grain (<10 μm) separates of three loess samples (Central Europe/NUS, China/BEI, USA/JUD) are presented. Good agreement between measured and reference Sr-Nd-Hf isotopic compositions (ICs) demonstrate that robust isotopic ratios can be obtained from 5 to 10 mg size rock samples using the ion exchange/mass spectrometry techniques applied. While 87Sr/86Sr ratios of dust aluminosilicate fractions are affected by even small changes in pretreatments, Nd isotopic ratios are found to be insensitive to acid leaching, grain-size or weathering effects. However, the Nd isotopic tracer is sometimes inconclusive in dust source fingerprinting (BEI and NUS both close to ɛNd(0) -10). Hafnium isotopic values (<10 μm fractions) are homogenous for NUS, while highly variable for BEI. This heterogeneity and vertical arrays of Hf isotopic data suggest zircon depletion effects toward the clay fractions (<2 μm). Monte Carlo simulations demonstrate that the Hf IC of the dust <10 μm fraction is influenced by both the abundance of zircons present and maturity of crustal rocks supplying this heavy mineral, while the <2 μm fraction is almost unaffected. Thus, ɛHf(0) variations in the clay fraction are largely controlled by the Hf IC of clays/heavy minerals having high Lu/Hf and radiogenic 176Hf/177Hf IC. Future work should be focused on Hf IC of both the <10 and <2 μm fractions of dust from potential source areas to gain more insight into the origin of last glacial dust in Greenland ice cores.

  13. Origin of isotopically light Zn in lunar samples through vaporization and the Zn isotope composition of the Moon

    NASA Astrophysics Data System (ADS)

    Kato, C.; Valdes, M. C.; Dhaliwal, J.; Day, J. M.; Moynier, F.

    2013-12-01

    The origin of the volatile element depletion of the Moon compared to Earth remains a key question in planetary science. It has recently been shown that both high-Ti and low-Ti lunar basalts are enriched in the heavier isotopes of Zn compared to Earth with an effect of ~1.3 permil on the 66Zn/64Zn ratio (Paniello et al., Nature, 2012). In order to obtain a better understanding of Zn behavior in and on the Moon, we present new measurements of lunar basalts, pyroclastic green glass 15426, highland anorthosites, cataclastic dunite 77215, cataclastic norite 72415 and some lunar soils. Samples were analyzed using a Thermo-Fisher Neptune Plus multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at Washington University in St Louis. The data presented below are reported as the permil deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard (δ66Zn). Four new high Ti basalts and three low Ti basalts confirm the observations of Paniello et al. (2012), that there is an enrichment in the heavier isotopes of Zn compared with chondrites and terrestrial samples. Combining these data together with Paniello et al. (2012) and Herzog et al. (GCA, 2009) we calculate a new average for lunar basalts of δ66Zn= 1.4×0.4 (1sd, n = 27). A few exceptions (5 samples out of 32) are isotopically light and probably represent addition of isotopically light Zn condensed onto the lunar surface from Zn isotopic fractionation during meteoritic impact, creating correspondingly isotopically heavy soils. In contrast to the homogeneity of mare basalts, highland samples show large Zn isotopic variability (δ66Zn -11.4 up to +4.24 permil) which encompasses the entire Zn isotopic variability measured so far in the Solar System. These δ66Zn variations are negatively correlated with the Zn abundance, with the isotopically light samples having the highest Zn concentrations. We interpret these results as the consequence of meteoritic bombardment and volatilization/condensation of Zn at

  14. Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

    USGS Publications Warehouse

    Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

    2012-01-01

    Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

  15. Isotopic Clues to Mars Crust-Atmosphere Interactions

    NASA Image and Video Library

    2016-09-29

    Chemistry that takes place in the surface material on Mars can explain why particular xenon (Xe) and krypton (Kr) isotopes are more abundant in the Martian atmosphere than expected. The isotopes -- variants that have different numbers of neutrons -- are formed in the loose rocks and material that make up the regolith -- the surface layer down to solid rock. The chemistry begins when cosmic rays penetrate into the surface material. If the cosmic rays strike an atom of barium (Ba), the barium can lose one or more of its neutrons (n0). Atoms of xenon can pick up some of those neutrons – a process called neutron capture – to form the isotopes xenon-124 and xenon-126. In the same way, atoms of bromine (Br) can lose some of their neutrons to krypton, leading to the formation of krypton-80 and krypton-82 isotopes. These isotopes can enter the atmosphere when the regolith is disturbed by impacts and abrasion, allowing gas to escape. http://photojournal.jpl.nasa.gov/catalog/PIA20847

  16. New approaches to the Moon's isotopic crisis.

    PubMed

    Melosh, H J

    2014-09-13

    Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth-Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  17. Intramolecular stable isotope distributions detect plant metabolic responses on century time scales

    NASA Astrophysics Data System (ADS)

    Schleucher, Jürgen; Ehlers, Ina; Augusti, Angela; Betson, Tatiana

    2014-05-01

    Plants respond to environmental changes on a vast range of time scales, and plant gas exchanges constitute important feedback mechanisms in the global C cycle. Responses on time scales of decades to centuries are most important for climate models, for prediction of crop productivity, and for adaptation to climate change. Unfortunately, responses on these timescale are least understood. We argue that the knowledge gap on intermediate time scales is due to a lack of adequate methods that can bridge between short-term manipulative experiments (e.g. FACE) and paleo research. Manipulative experiments in plant ecophysiology give information on metabolism on time scales up to years. However, this information cannot be linked to results from retrospective studies in paleo research, because little metabolic information can be derived from paleo archives. Stable isotopes are prominent tools in plant ecophysiology, biogeochemistry and in paleo research, but in all applications to date, isotope ratios of whole molecules are measured. However, it is well established that stable isotope abundance varies among intramolecular groups of biochemical metabolites, that is each so-called "isotopomer" has a distinct abundance. This intramolecular variation carries information on metabolic regulation, which can even be traced to individual enzymes (Schleucher et al., Plant, Cell Environ 1999). Here, we apply intramolecular isotope distributions to study the metabolic response of plants to increasing atmospheric [CO2] during the past century. Greenhouse experiments show that the deuterium abundance among the two positions in the C6H2 group of photosynthetic glucose depends on [CO2] during growth. This is observed for all plants using C3 photosynthesis, and reflects the metabolic flux ratio between photorespiration and photosynthesis. Photorespiration is a major C flux that limits assimilation in C3 plants, which encompass the overwhelming fraction of terrestrial photosynthesis and the

  18. 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

  19. Stable Isotope Identification of Nitrogen Sources for United States (U.S.) Pacific Coast Estuaries

    EPA Science Inventory

    We used natural abundance stable isotope data to evaluate nitrogen sources to U.S. west coast estuaries. We collected δ15N of macroalgae data and supplemented this with available data from the literature for estuaries from Mexico to Alaska. Stable isotope ratios of green m...

  20. Environmental isotope investigation of groundwater flow in the Honey Lake Basin, California and Nevada

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

    Rose, T.P.; Davisson, M.L.; Hudson, G.B.

    The hydrology of Honey Lake Basin was studied using environmental isotope measurements of approximately 130 water samples collected during 1995 and 1996. The principal analytical methods included hydrogen, oxygen and carbon stable isotope ratio measurements, radiocarbon and tritium dating, and measurements of dissolved noble gas abundances.

  1. NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Stadermann, F. J.; Croat, T. K.; Bernatowicz, T.

    2004-01-01

    Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

  2. Monte Carlo isotopic inventory analysis for complex nuclear systems

    NASA Astrophysics Data System (ADS)

    Phruksarojanakun, Phiphat

    Monte Carlo Inventory Simulation Engine (MCise) is a newly developed method for calculating isotopic inventory of materials. It offers the promise of modeling materials with complex processes and irradiation histories, which pose challenges for current, deterministic tools, and has strong analogies to Monte Carlo (MC) neutral particle transport. The analog method, including considerations for simple, complex and loop flows, is fully developed. In addition, six variance reduction tools provide unique capabilities of MCise to improve statistical precision of MC simulations. Forced Reaction forces an atom to undergo a desired number of reactions in a given irradiation environment. Biased Reaction Branching primarily focuses on improving statistical results of the isotopes that are produced from rare reaction pathways. Biased Source Sampling aims at increasing frequencies of sampling rare initial isotopes as the starting particles. Reaction Path Splitting increases the population by splitting the atom at each reaction point, creating one new atom for each decay or transmutation product. Delta Tracking is recommended for high-frequency pulsing to reduce the computing time. Lastly, Weight Window is introduced as a strategy to decrease large deviations of weight due to the uses of variance reduction techniques. A figure of merit is necessary to compare the efficiency of different variance reduction techniques. A number of possibilities for figure of merit are explored, two of which are robust and subsequently used. One is based on the relative error of a known target isotope (1/R 2T) and the other on the overall detection limit corrected by the relative error (1/DkR 2T). An automated Adaptive Variance-reduction Adjustment (AVA) tool is developed to iteratively define parameters for some variance reduction techniques in a problem with a target isotope. Sample problems demonstrate that AVA improves both precision and accuracy of a target result in an efficient manner

  3. Estimating abundance

    USGS Publications Warehouse

    Sutherland, Chris; Royle, Andy

    2016-01-01

    This chapter provides a non-technical overview of ‘closed population capture–recapture’ models, a class of well-established models that are widely applied in ecology, such as removal sampling, covariate models, and distance sampling. These methods are regularly adopted for studies of reptiles, in order to estimate abundance from counts of marked individuals while accounting for imperfect detection. Thus, the chapter describes some classic closed population models for estimating abundance, with considerations for some recent extensions that provide a spatial context for the estimation of abundance, and therefore density. Finally, the chapter suggests some software for use in data analysis, such as the Windows-based program MARK, and provides an example of estimating abundance and density of reptiles using an artificial cover object survey of Slow Worms (Anguis fragilis).

  4. Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

    1995-01-01

    Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

  5. Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Kimura, Makoto; El-Goresy, Ahmed; Palme, Herbert; Zinner, Ernst

    1993-01-01

    A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

  6. Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

    2013-01-01

    The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

  7. Hydrogeochemistry and quality of surface water and groundwater in the vicinity of Lake Monoun, West Cameroon: approach from multivariate statistical analysis and stable isotopic characterization.

    PubMed

    Kamtchueng, Brice T; Fantong, Wilson Y; Wirmvem, Mengnjo J; Tiodjio, Rosine E; Takounjou, Alain F; Ndam Ngoupayou, Jules R; Kusakabe, Minoru; Zhang, Jing; Ohba, Takeshi; Tanyileke, Gregory; Hell, Joseph V; Ueda, Akira

    2016-09-01

    With the use of conventional hydrogeochemical techniques, multivariate statistical analysis, and stable isotope approaches, this paper investigates for the first time surface water and groundwater from the surrounding areas of Lake Monoun (LM), West Cameroon. The results reveal that waters are generally slightly acidic to neutral. The relative abundance of major dissolved species are Ca(2+) > Mg(2+) > Na(+) > K(+) for cations and HCO3 (-) ≫ NO3 (-) > Cl(-) > SO4 (2-) for anions. The main water type is Ca-Mg-HCO3. Observed salinity is related to water-rock interaction, ion exchange process, and anthropogenic activities. Nitrate and chloride have been identified as the most common pollutants. These pollutants are attributed to the chlorination of wells and leaching from pit latrines and refuse dumps. The stable isotopic compositions in the investigated water sources suggest evidence of evaporation before recharge. Four major groups of waters were identified by salinity and NO3 concentrations using the Q-mode hierarchical cluster analysis (HCA). Consistent with the isotopic results, group 1 represents fresh unpolluted water occurring near the recharge zone in the general flow regime; groups 2 and 3 are mixed water whose composition is controlled by both weathering of rock-forming minerals and anthropogenic activities; group 4 represents water under high vulnerability of anthropogenic pollution. Moreover, the isotopic results and the HCA showed that the CO2-rich bottom water of LM belongs to an isolated hydrological system within the Foumbot plain. Except for some springs, groundwater water in the area is inappropriate for drinking and domestic purposes but good to excellent for irrigation.

  8. First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi

    PubMed Central

    Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

    2015-01-01

    Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass (Equus hemionus) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi. PMID:26339116

  9. First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi.

    PubMed

    Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

    Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass ( Equus hemionus ) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi.

  10. In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

    PubMed

    Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

    2017-12-19

    Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

  11. In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

    NASA Astrophysics Data System (ADS)

    Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

    2016-06-01

    Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

  12. 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.

  13. Coupled micromorphological and stable isotope analysis of Quaternary calcrete development

    NASA Astrophysics Data System (ADS)

    Adamson, Kathryn; Candy, Ian; Whitfield, Liz

    2015-09-01

    Pedogenic calcretes are widespread in arid and semi-arid regions. Using calcrete profiles from four river terraces of the Rio Alias in southeast Spain, this study explores the potential of using detailed micromorphological and stable isotopic analysis to more fully understand the impacts of Quaternary environmental change on calcrete development. The four profiles increase in carbonate complexity with progressive age, reflecting calcretisation over multiple glacial-interglacial cycles since MIS 9 (c. 300 ka). Calcrete profiles contain a mixture of Alpha (non-biogenic) and Beta (biogenic) microfabrics. Alpha fabrics have higher δ13C and δ18O values. The profiles contain a range of crystal textures, but there is little difference between the δ13C and δ18O values of spar, microspar, and micrite cements. Strong positive covariance between δ13C and δ18O suggests that both isotopes are responding to the same environmental parameter, which is inferred to be relative aridity. The study reveals that the detailed co-analysis of calcrete micromorphology and stable isotope signatures can allow patterns of calcrete formation to be placed into a wider palaeoclimatic context. This demonstrates the potential of this technique to more reliably constrain the palaeoenvironmental significance of secondary carbonates in dryland settings where other proxy records may be poorly preserved.

  14. Characterization of phenols biodegradation by compound specific stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    -cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

  15. Stable-isotope analysis: a neglected tool for placing parasites in food webs.

    PubMed

    Sabadel, A J M; Stumbo, A D; MacLeod, C D

    2018-02-28

    Parasites are often overlooked in the construction of food webs, despite their ubiquitous presence in almost every type of ecosystem. Researchers who do recognize their importance often struggle to include parasites using classical food-web theory, mainly due to the parasites' multiple hosts and life stages. A novel approach using compound-specific stable-isotope analysis promises to provide considerable insight into the energetic exchanges of parasite and host, which may solve some of the issues inherent in incorporating parasites using a classical approach. Understanding the role of parasites within food webs, and tracing the associated biomass transfers, are crucial to constructing new models that will expand our knowledge of food webs. This mini-review focuses on stable-isotope studies published in the past decade, and introduces compound-specific stable-isotope analysis as a powerful, but underutilized, newly developed tool that may answer many unresolved questions regarding the role of parasites in food webs.

  16. Evaluation of stable isotope fingerprinting techniques for the assessment of the predominant methanogenic pathways in anaerobic digesters.

    PubMed

    Nikolausz, M; Walter, R F H; Sträuber, H; Liebetrau, J; Schmidt, T; Kleinsteuber, S; Bratfisch, F; Günther, U; Richnow, H H

    2013-03-01

    Laboratory biogas reactors were operated under various conditions using maize silage, chicken manure, or distillers grains as substrate. In addition to the standard process parameters, the hydrogen and carbon stable isotopic composition of biogas was analyzed to estimate the predominant methanogenic pathways as a potential process control tool. The isotopic fingerprinting technique was evaluated by parallel analysis of mcrA genes and their transcripts to study the diversity and activity of methanogens. The dominant hydrogenotrophs were Methanomicrobiales, while aceticlastic methanogens were represented by Methanosaeta and Methanosarcina at low and high organic loading rates, respectively. Major changes in the relative abundance of mcrA transcripts were observed compared to the results obtained from DNA level. In agreement with the molecular results, the isotope data suggested the predominance of the hydrogenotrophic pathway in one reactor fed with chicken manure, while both pathways were important in the other reactors. Short-term changes in the isotopic composition were followed, and a significant change in isotope values was observed after feeding a reactor digesting maize silage. This ability of stable isotope fingerprinting to follow short-term activity changes shows potential for indicating process failures and makes it a promising technology for process control.

  17. Abundance Analysis of 17 Planetary Nebulae from High-Resolution Optical Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sherrard, Cameroun G.; Sterling, Nicholas C.; Dinerstein, Harriet L.; Madonna, Simone; Mashburn, Amanda

    2017-06-01

    We present an abundance analysis of 17 planetary nebulae (PNe) observed with the 2D-coudé echelle spectrograph on the 2.7-m Harlan J. Smith telescope at McDonald Observatory. The spectra cover the wavelength range 3600--10,400 Å at a resolution R = 36,700, and are the first high-resolution optical spectra for many objects in our sample. The number of emission lines detected in individual nebulae range from ~125 to over 600. We derive temperatures, densities, and abundances from collisionally-excited lines using the PyNeb package (Luridiana et al. 2015, A&A, 573, A42) and the ionization correction factor scheme of Delgado-Inglada et al. (2014, MNRAS, 440, 536). The abundances of light elements agree with previous estimates for most of the PNe. Several objects exhibit emission lines of refractory elements such as K and Fe, and neutron-capture elements that can be enriched by the s-process. We find that K and Fe are depleted relative to solar by ~0.3--0.7~dex and 1-2 dex, respectively, and find evidence for s-process enrichments in 10 objects. Several objects in our sample exhibit C, N, and O recombination lines that are useful for abundance determinations. These transitions are used to compute abundance discrepancy factors (ADFs), the ratio of ionic abundances derived from permitted lines to those from collisionally-excited transitions. We explore relations among depletion factors, ADFs, s-process enrichment factors, and other nebular stellar and nebular properties. We acknowledge support from NSF awards AST-901432 and AST-0708429.

  18. Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

    NASA Astrophysics Data System (ADS)

    Billmark, K. A.; Macko, S. A.; Swap, R. J.

    2003-12-01

    This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

  19. Chromium isotopic anomalies in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.

    1986-01-01

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

  20. Study of the isotopic features of Swan bands in comets

    NASA Technical Reports Server (NTRS)

    Krishna Swamy, K. S.

    1987-01-01

    It is shown from a detailed statistical equilibrium calculation of the (C-12)(C-13) molecule that the interpretation of the observed intensities of Swan bands of the normal and the isotopic molecule of C2 in terms of the abundance ratio of C-12 and C-13 is a reasonable one. The synthetic profile of some isotopic features in the (0.0) Swan band is compared with the observed profiles for comet West.

  1. NEON AND CNO ABUNDANCES FOR EXTREME HELIUM STARS-A NON-LTE ANALYSIS

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

    Pandey, Gajendra; Lambert, David L., E-mail: pandey@iiap.res.in, E-mail: dll@astro.as.utexas.edu

    A non-LTE (NLTE) abundance analysis was carried out for three extreme helium stars (EHes): BD+10{sup 0} 2179, BD-9{sup 0} 4395, and LS IV+6{sup 0} 002, from their optical spectra with NLTE model atmospheres. NLTE TLUSTY model atmospheres were computed with H, He, C, N, O, and Ne treated in NLTE. Model atmosphere parameters were chosen from consideration of fits to observed He I line profiles and ionization equilibria of C and N ions. The program SYNSPEC was then used to determine the NLTE abundances for Ne as well as H, He, C, N, and O. LTE neon abundances from Nemore » I lines in the EHes: LSE 78, V1920 Cyg, HD 124448, and PV Tel, are derived from published models and an estimate of the NLTE correction applied to obtain the NLTE Ne abundance. We show that the derived abundances of these key elements, including Ne, are well matched with semi-quantitative predictions for the EHe resulting from a cold merger (i.e., no nucleosynthesis during the merger) of an He white dwarf with a C-O white dwarf.« less

  2. Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

    NASA Astrophysics Data System (ADS)

    Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

    2013-04-01

    Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation

  3. ``Recycling'' Geophysics: Monitoring and Isotopic Analysis of Engineered Biological Systems

    NASA Astrophysics Data System (ADS)

    Doherty, R.; Singh, K. P.; Ogle, N.; Ntarlagiannis, D.

    2010-12-01

    The emerging sub discipline of biogeophysics has provoked debate on the mechanisms of microbial processes that may contribute to geophysical signatures. At field scales geophysical signatures are often non unique due to the many parameters (physical, chemical, and biological) that are involved. It may be easier to apply geophysical techniques such as electrodic potential (EP), self potential (SP) and induced polarization (IP) to engineered biological systems where there is a degree of control over the design of the physical and chemical domain. Here we present results of a column experiment that was designed to anaerobically biodegrade dissolved organic matter in landfill leachate. The column utilises a recycled porous media (concrete) to help sequester organic carbon. Electrodic potential, self potential and induced polarisation are used in conjunction with chemical and isotopic techniques to monitor the effectiveness of this approach. Preliminary carbon and oxygen isotopic analysis on concrete from the column in contact with leachate show isotopic enrichment suggesting abiotic precipitation of carbonates.

  4. Body temperatures of modern and extinct vertebrates from 13C-18O bond abundances in bioapatite

    PubMed Central

    Eagle, Robert A.; Schauble, Edwin A.; Tripati, Aradhna K.; Tütken, Thomas; Hulbert, Richard C.; Eiler, John M.

    2010-01-01

    The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms and to reconstruct past climate. Here we report the application of a new type of geochemical measurement to bioapatite, a “clumped-isotope” paleothermometer, based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the bioapatite crystal lattice. This effect is dependent on temperature but, unlike conventional stable isotope paleothermometers, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of tooth bioapatite from modern specimens decreases with increasing body temperature of the animal, following a relationship between isotope “clumping” and temperature that is statistically indistinguishable from inorganic calcite. This result is in agreement with a theoretical model of isotopic ordering in carbonate ion groups in apatite and calcite. This thermometer constrains body temperatures of bioapatite-producing organisms with an accuracy of 1–2 °C. Analyses of fossilized tooth enamel of both Pleistocene and Miocene age yielded temperatures within error of those derived from similar modern taxa. Clumped-isotope analysis of bioapatite represents a new approach in the study of the thermophysiology of extinct species, allowing the first direct measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurement of clumped isotopes in phosphorites and fossils has the potential to reconstruct environmental temperatures. PMID:20498092

  5. 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.

  6. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

    Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  7. OXYGEN ABUNDANCES IN CEPHEIDS

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

    Luck, R. E.; Andrievsky, S. M.; Korotin, S. N.

    2013-07-01

    Oxygen abundances in later-type stars, and intermediate-mass stars in particular, are usually determined from the [O I] line at 630.0 nm, and to a lesser extent, from the O I triplet at 615.7 nm. The near-IR triplets at 777.4 nm and 844.6 nm are strong in these stars and generally do not suffer from severe blending with other species. However, these latter two triplets suffer from strong non-local thermodynamic equilibrium (NLTE) effects and thus see limited use in abundance analyses. In this paper, we derive oxygen abundances in a large sample of Cepheids using the near-IR triplets from an NLTEmore » analysis, and compare those abundances to values derived from a local thermodynamic equilibrium (LTE) analysis of the [O I] 630.0 nm line and the O I 615.7 nm triplet as well as LTE abundances for the 777.4 nm triplet. All of these lines suffer from line strength problems making them sensitive to either measurement complications (weak lines) or to line saturation difficulties (strong lines). Upon this realization, the LTE results for the [O I] lines and the O I 615.7 nm triplet are in adequate agreement with the abundance from the NLTE analysis of the near-IR triplets.« less

  8. Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis

    NASA Astrophysics Data System (ADS)

    Horváth, Anikó; Futó, István; Palcsu, László

    2014-05-01

    Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.

  9. Methylamphetamine synthesized from cold medication as precursor source via two different routes show significantly different stable isotope signatures

    NASA Astrophysics Data System (ADS)

    Jayaram, S.; Daeid, N. Nic; Kerr, W. J.; Kemp, H. F.; Meier-Augenstein, W.

    2012-04-01

    This work exposes the variation in light element stable isotopic abundance values of 13C, 2H and 15N) derived from the analysis of methylamphetamine synthesized via 2 different synthetic routes popular with clandestine laboraties, the Hypophosphorous and the Moscow route. We repeatedly prepared the final product using known clandestine synthetic methods where the precursors, catalysts and reducing agents have themselves been derived from house hold products and commonly available cold medications. Methylamphetamine was prepared from both lab grade pseudoephedrine and pseudoephedrine extracted (using three different solvent systems) from Sudafed®, an over-the-counter cold medication widely available in the United Kingdom. Six repetitive batches of the final product were produced in each case to provide within and between batch variations thus yielding a total of 48 samples (24 for each route). We have demonstrated that stable isotope analysis by Isotope Ratio Mass Spectrometry (IRMS) is potentially useful in the comparison and discrimination of batches of methylamphetamine produced for each route and for each precursor depending on the solvent used for extracting the pseudoephedrine starting material. To our knowledge this is the first time multivariate stable isotope analysis has been applied to methylamphetamine samples synthesized from pseudoephedrine extracted from over-the-counter cold medications.

  10. Analysis of the differentially expressed low molecular weight peptides in human serum via an N-terminal isotope labeling technique combining nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Leng, Jiapeng; Zhu, Dong; Wu, Duojiao; Zhu, Tongyu; Zhao, Ningwei; Guo, Yinlong

    2012-11-15

    Peptidomics analysis of human serum is challenging due to the low abundance of serum peptides and interference from the complex matrix. This study analyzed the differentially expressed (DE) low molecular weight peptides in human serum integrating a DMPITC-based N-terminal isotope labeling technique with nano-liquid chromatography and matrix-assisted laser desorption/ionization mass spectrometry (nano-LC/MALDI-MS). The workflow introduced a [d(6)]-4,6-dimethoxypyrimidine-2-isothiocyanate (DMPITC)-labeled mixture of aliquots from test samples as the internal standard. The spiked [d(0)]-DMPITC-labeled samples were separated by nano-LC then spotted on the MALDI target. Both quantitative and qualitative studies for serum peptides were achieved based on the isotope-labeled peaks. The DMPITC labeling technique combined with nano-LC/MALDI-MS not only minimized the errors in peptide quantitation, but also allowed convenient recognition of the labeled peptides due to the 6 Da mass difference. The data showed that the entire research procedure as well as the subsequent data analysis method were effective, reproducible, and sensitive for the analysis of DE serum peptides. This study successfully established a research model for DE serum peptides using DMPITC-based N-terminal isotope labeling and nano-LC/MALDI-MS. Application of the DMPITC-based N-terminal labeling technique is expected to provide a promising tool for the investigation of peptides in vivo, especially for the analysis of DE peptides under different biological conditions. Copyright © 2012 John Wiley & Sons, Ltd.

  11. A new method of tree xylem water extraction for isotopic analysis

    NASA Astrophysics Data System (ADS)

    Gierke, C.; Newton, B. T.

    2011-12-01

    The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial

  12. Asymptotic Analysis of Time-Dependent Neutron Transport Coupled with Isotopic Depletion and Radioactive Decay

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

    Brantley, P S

    2006-09-27

    We describe an asymptotic analysis of the coupled nonlinear system of equations describing time-dependent three-dimensional monoenergetic neutron transport and isotopic depletion and radioactive decay. The classic asymptotic diffusion scaling of Larsen and Keller [1], along with a consistent small scaling of the terms describing the radioactive decay of isotopes, is applied to this coupled nonlinear system of equations in a medium of specified initial isotopic composition. The analysis demonstrates that to leading order the neutron transport equation limits to the standard time-dependent neutron diffusion equation with macroscopic cross sections whose number densities are determined by the standard system of ordinarymore » differential equations, the so-called Bateman equations, describing the temporal evolution of the nuclide number densities.« less

  13. Online analysis of chlorine stable isotopes in chlorinated ethylenes: an inter-laboratory study

    NASA Astrophysics Data System (ADS)

    Bernstein, Anat; Shouakar-Stash, Orfan; Hunkeler, Daniel; Sakaguchi-Söder, Kaori; Laskov, Christine; Aravena, Ramon; Elsner, Martin

    2010-05-01

    In the last decade, compound-specific stable isotopes analysis of groundwater pollutants became an important tool to identify different sources of the same pollutant and for tracking natural attenuating processes in the sub-surface. It has been shown that trends in the isotopic composition of the target compounds can shed light on in-situ processes that are otherwise difficult to track. Analytical methods of carbon, nitrogen and hydrogen were established and are by now frequently used for a variety of organic pollutants. Yet, the motivation of introducing analytical methods for new isotopes is emerging. This motivation is further enhanced, as advantages of using two or more stable isotopes for gaining better insight on degradation pathways are well accepted. One important element which demands the development of appropriate analytical methods is chlorine, which is found in various groups of organic pollutants, among them the chlorinated ethylenes. Chlorinated ethylenes are considered as high priority environmental pollutants, and the development of suitable chlorine isotope methods for this group of pollutants is highly desired. Ideally, stable isotope techniques should have the capability to determine the isotopic composition of and individual target compound in a non-pure mixture, without the requirement of a laborious off-line treatment. Indeed, in the last years two different concepts for on-line chlorine isotope analysis methods were introduced, by using either a standard quadrapole GC/MS (Sakaguchi-Söder et al., 2007) or by using a GC/IRMS (Shouakar-Stash et al., 2006). We present a comparison of the performances of two concepts, carried out in five different laboratories: Waterloo (GC/IRMS), Neuchâtel (GC/MS), Darmstadt (GC/MS), Tübingen (GC/MS) and Munich (GC/IRMS). This comparison was performed on pure trichloroethylene and dichloroethylene products of different manufactures, as well as trichloroethylene and dichloroethylene samples that were exposed to

  14. Development of a compound-specific isotope analysis method for acetone via 2,4-dinitrophenylhydrazine derivatization.

    PubMed

    Wen, Sheng; Feng, Yanli; Wang, Xinming; Sheng, Guoying; Fu, Jiamo; Bi, Xinhui

    2004-01-01

    A novel method has been developed for compound-specific isotope analysis for acetone via DNPH (2,4-dinitrophenylhydrazine) derivatization together with combined gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Acetone reagents were used to assess delta13C fractionation during the DNPH derivatization process. Reduplicate delta13C analyses were designed to evaluate the reproducibility of the derivatization, with an average error (1 standard deviation) of 0.17 +/- 0.05 per thousand, and average analytical error of 0.28 +/- 0.09 per thousand. The derivatization process introduces no isotopic fractionation for acetone (the average difference between the predicted and analytical delta13C values was 0.09 +/- 0.20 per thousand, within the precision limits of the GC/C/IRMS measurements), which permits computation of the delta13C values for the original underivatized acetone through a mass balance equation. Together with further studies of the carbon isotopic effect during the atmospheric acetone-sampling procedure, it will be possible to use DNPH derivatization for carbon isotope analysis of atmospheric acetone. Copyright (c) 2004 John Wiley & Sons, Ltd.

  15. Project VeSElkA: results of abundance analysis for HD 53929 and HD 63975

    NASA Astrophysics Data System (ADS)

    Ndiaye, M. L.; LeBlanc, F.; Khalack, V.

    2018-03-01

    Project VeSElkA (Vertical Stratification of Element Abundances) has been initiated with the aim to detect and study the vertical stratification of element abundances in the atmosphere of chemically peculiar stars. Abundance stratification occurs in hydrodynamically stable stellar atmospheres due to the migration of the elements caused by atomic diffusion. Two HgMn stars, HD 53929 and HD 63975 were selected from the VeSElkA sample and analysed with the aim to detect some abundance peculiarities employing the ZEEMAN2 code. We present the results of abundance analysis of HD 53929 and HD 63975 observed recently with the spectropolarimeter ESPaDOnS at Canada-France-Hawaii Telescope. Evidence of phosphorus vertical stratification was detected in the atmosphere of these two stars. In both cases, phosphorus abundance increases strongly towards the superficial layers. The strong overabundance of Mn found in stellar atmosphere of both stars confirms that they are HgMn type stars.

  16. Matrix Effects on Boron Containing Materials due to Laser Ablation Molecular Isotopic Spectrometry (LAMIS)

    NASA Astrophysics Data System (ADS)

    Brown, Staci R.; Akpovo, Charlemagne A.; Martinez, Jorge; Ford, Alan; Herbert, Kenley; Johnson, Lewis

    2014-03-01

    Laser Induced Breakdown Spectroscopy (LIBS) is a spectroscopic technique that is used for the qualitative and quantitative analysis of materials in the liquid, solid, or gas phase. LIBS can also be used for the detection of isotopic shifts in atomic and diatomic species via Laser-Ablation Molecular Isotopic Spectroscopy (LAMIS). However, any additional elements that are entrained into the plasma other than the element of interest, can affect the extent of ablation and quality of spectra and hence, potentially obscure or aid in the relative abundance assessment for a given element. To address the importance of matrix effects, the isotopic analysis of boron obtained from boron oxide (BO) emission originating from different boron-containing compounds, such as boron nitride (BN), boric acid (H3BO3) , and borax (Na2B4O710H2O), via LIBS has been performed here. Each of these materials has different physical properties and elemental composition in order to illustrate possible challenges for the LAMIS method. A calibration-free model similar to that for the original LAMIS work is used to determine properties of the plasma as the matrix is changed. DTRA

  17. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Cristea, G.; Cordea, D. V.; Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Mihaiu, M.

    2013-11-01

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ18O and δ2H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ18O and δ2H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  18. Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

    USGS Publications Warehouse

    Coplen, Tyler B.

    2011-01-01

    To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

  19. ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

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

    Sakai, H.; Sato, K.

    1958-11-01

    Lead tetramethyl was synthesized from lead iodide isolated from 14 galenas, 2 anglesites, and 6 pyromorphites of Japan. The mass spectrometric analysis was carried out for the peaks of lead and lead hydride ions. The isotopic compositions of leads from these minerais lie wiyhn a narrow range. The average values for gnlanas are 18.51 O 0.05 for Pb/sup 238//Pb/sup 204/ 15.60 plus or minus 0.05 for Pb/sup 207//Pb/sup 204/8.76 plus or minus 0.15 forPb/ sup 208//Pb/sup 204/ For lead of secondary minerals they are 18.52 plus or minus 0.05, 15.62 plus or minus 0.05, and 38.78 plus or minus 0.15,more » respectively. No detectabla difference was observed between the isotopic compositions of primary and secondary lead ores. The ratios, U/sub 238/Pb/sup 204, and Th/sup 232/ U/sup 238/, in the source magma are estimated from the lead abundances. They are« less

  20. Isotope analysis reveals foraging area dichotomy for atlantic leatherback turtles.

    PubMed

    Caut, Stéphane; Fossette, Sabrina; Guirlet, Elodie; Angulo, Elena; Das, Krishna; Girondot, Marc; Georges, Jean-Yves

    2008-03-26

    The leatherback turtle (Dermochelys coriacea) has undergone a dramatic decline over the last 25 years, and this is believed to be primarily the result of mortality associated with fisheries bycatch followed by egg and nesting female harvest. Atlantic leatherback turtles undertake long migrations across ocean basins from subtropical and tropical nesting beaches to productive frontal areas. Migration between two nesting seasons can last 2 or 3 years, a time period termed the remigration interval (RI). Recent satellite transmitter data revealed that Atlantic leatherbacks follow two major dispersion patterns after nesting season, through the North Gulf Stream area or more eastward across the North Equatorial Current. However, information on the whole RI is lacking, precluding the accurate identification of feeding areas where conservation measures may need to be applied. Using stable isotopes as dietary tracers we determined the characteristics of feeding grounds of leatherback females nesting in French Guiana. During migration, 3-year RI females differed from 2-year RI females in their isotope values, implying differences in their choice of feeding habitats (offshore vs. more coastal) and foraging latitude (North Atlantic vs. West African coasts, respectively). Egg-yolk and blood isotope values are correlated in nesting females, indicating that egg analysis is a useful tool for assessing isotope values in these turtles, including adults when not available. Our results complement previous data on turtle movements during the first year following the nesting season, integrating the diet consumed during the year before nesting. We suggest that the French Guiana leatherback population segregates into two distinct isotopic groupings, and highlight the urgent need to determine the feeding habitats of the turtle in the Atlantic in order to protect this species from incidental take by commercial fisheries. Our results also emphasize the use of eggs, a less-invasive sampling

  1. Enantiomeric and Isotopic Analysis of Sugar Derivatives in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George; Asiyo, Cynthia; Turk, Kendra; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    Several classes of organic compounds are found in carbonaceous meteorites including amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in the origin of life. Likewise, sugar derivatives are critical to all known lifeforms. Recent analyses of the Murchison and Murray carbonaceous meteorites revealed a diverse suite of such derivatives, i.e., sugar alcohols, and sugar acids. This presentation will focus primarily on the analysis of individual sugar acids - their enantiomeric and isotopic composition. Analysis of these compounds may reveal the nature of past (or present) meteoritic sugars themselves. For example, if parent sugars decomposed (by well-known mechanisms) to give the present acids, were their enantiomeric ratios preserved? Combined with other evidence, the enantiomeric composition of such compounds as glyceric acid and (especially) rare acids may help to answer such questions. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) as a group revealed that they were indigenous to the meteorite. Preliminary C-13 analysis of glyceric acid shows that it is also extraterrestrial.

  2. Suitability of selected free-gas and dissolved-gas sampling containers for carbon isotopic analysis.

    PubMed

    Eby, P; Gibson, J J; Yi, Y

    2015-07-15

    Storage trials were conducted for 2 to 3 months using a hydrocarbon and carbon dioxide gas mixture with known carbon isotopic composition to simulate typical hold times for gas samples prior to isotopic analysis. A range of containers (both pierced and unpierced) was periodically sampled to test for δ(13)C isotopic fractionation. Seventeen containers were tested for free-gas storage (20°C, 1 atm pressure) and 7 containers were tested for dissolved-gas storage, the latter prepared by bubbling free gas through tap water until saturated (20°C, 1 atm) and then preserved to avoid biological activity by acidifying to pH 2 with phosphoric acid and stored in the dark at 5°C. Samples were extracted using valves or by piercing septa, and then introduced into an isotope ratio mass spectrometer for compound-specific δ(13)C measurements. For free gas, stainless steel canisters and crimp-top glass serum bottles with butyl septa were most effective at preventing isotopic fractionation (pierced and unpierced), whereas silicone and PTFE-butyl septa allowed significant isotopic fractionation. FlexFoil and Tedlar bags were found to be effective only for storage of up to 1 month. For dissolved gas, crimp-top glass serum bottles with butyl septa were again effective, whereas silicone and PTFE-butyl were not. FlexFoil bags were reliable for up to 2 months. Our results suggest a range of preferred containers as well as several that did not perform very well for isotopic analysis. Overall, the results help establish better QA/QC procedures to avoid isotopic fractionation when storing environmental gas samples. Recommended containers for air transportation include steel canisters and glass serum bottles with butyl septa (pierced and unpierced). Copyright © 2015 John Wiley & Sons, Ltd.

  3. Proteomic analysis of common bean stem under drought stress using in-gel stable isotope labeling.

    PubMed

    Zadražnik, Tanja; Egge-Jacobsen, Wolfgang; Meglič, Vladimir; Šuštar-Vozlič, Jelka

    2017-02-01

    Drought is an abiotic stress that strongly influences plant growth, development and productivity. Proteome changes in the stem of the drought-tolerant common bean (Phaseolus vulgaris L.) cultivar Tiber have were when the plants were exposed to drought. Five-week-old plants were subjected to water deficit by withholding irrigation for 7, 12 and 17days, whereas control plants were regularly irrigated. Relative water content (RWC) of leaves, as an indicator of the degree of cell and tissue hydration, showed the highest statistically significant differences between control and drought-stressed plants after 17days of treatment, where RWC remained at 90% for control and declined to 45% for stressed plants. Plants exposed to drought for 17days and control plants at the same developmental stage were included in quantitative proteomic analysis using in-gel stable isotope labeling of proteins in combination with mass spectrometry. The quantified proteins were grouped into several functional groups, mainly into energy metabolism, photosynthesis, proteolysis, protein synthesis and proteins related to defense and stress. 70kDa heat shock protein showed the greatest increase in abundance under drought of all the proteins, suggesting its role in protecting plants against stress by re-establishing normal protein conformations and thus cellular homeostasis. The abundance of proteins involved in protein synthesis also increased under drought stress, important for recovery of damaged proteins involved in the plant cell's metabolic activities. Other important proteins in this study were related to proteolysis and folding, which are necessary for maintaining proper cellular protein homeostasis. Taken together, these results reveal the complexity of pathways involved in the drought stress response in common bean stems and enable comparison with the results of proteomic analysis of leaves, thus providing important information to further understand the biochemical and molecular mechanisms

  4. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

  5. High-resolution abundance analysis of the metallic-line star HR 7250

    NASA Astrophysics Data System (ADS)

    Elmaslı, Aslı; Ünal, Kübraözge; Çalışkan, Şeyma

    2018-07-01

    We estimated the stellar parameters and chemical abundances of the highly neglected A-type star HR 7250. The star's high resolution spectrum, spanning a wavelength range from 3900 to 7900 Å, was obtained at the TÜBİTAK National Observatory. We derived the abundances of 14 elements (O, Na, Mg, Si, S, Ca, Sc, Ti, Cr, Fe, Ni, Sr, Y, and Ba) for HR 7250 from the unblended lines of the star's spectrum. Our analysis shows that HR 7250 is a chemically peculiar Am star. We also estimated its age and mass as 400 ± 70 Myr and 3.25 ± 0.17 M⊙ from evolutionary tracks and isochrones.

  6. Changes in carbon sources fueling benthic secondary production over depth and time: coupling Chironomidae stable carbon isotopes to larval abundance.

    PubMed

    Frossard, Victor; Verneaux, Valérie; Millet, Laurent; Magny, Michel; Perga, Marie-Elodie

    2015-06-01

    Stable C isotope ratio (δ(13)C) values of chironomid remains (head capsules; HC) were used to infer changes in benthic C sources over the last 150 years for two French sub-Alpine lakes. The HCs were retrieved from a series of sediment cores from different depths. The HC δ(13)C values started to decrease with the onset of eutrophication. The HC δ(13)C temporal patterns varied among depths, which revealed spatial differences in the contribution of methanotrophic bacteria to the benthic secondary production. The estimates of the methane (CH4)-derived C contribution to chironomid biomass ranged from a few percent prior to the 1930s to up to 30 % in recent times. The chironomid fluxes increased concomitantly with changes in HC δ(13)C values before a drastic decrease due to the development of hypoxic conditions. The hypoxia reinforced the implication for CH4-derived C transfer to chironomid production. In Lake Annecy, the HC δ(13)C values were negatively correlated to total organic C (TOC) content in the sediment (Corg), whereas no relationship was found in Lake Bourget. In Lake Bourget, chironomid abundances reached their maximum with TOC contents between 1 and 1.5 % Corg, which could constitute a threshold for change in chironomid abundance and consequently for the integration of CH4-derived C into the lake food webs. Our results indicated that the CH4-derived C contribution to the benthic food webs occurred at different depths in these two large, deep lakes (deep waters and sublittoral zone), and that the trophic transfer of this C was promoted in sublittoral zones where O2 gradients were dynamic.

  7. Trophic spectra under the lens of amino acid isotopic analysis

    USDA-ARS?s Scientific Manuscript database

    Recent advances in compound specific isotopic ratio analysis (CSIRA) have allowed researchers to measure trophic fractionation of 15N in specific amino acids, namely glutamic acid and phenylalanine. These amino acids have proven useful in food web studies because of the wide and consistent disparity...

  8. Segregation of isotopes of heavy metals due to light-induced drift: results and problems

    NASA Astrophysics Data System (ADS)

    Sapar, A.; Aret, A.; Poolamäe, R.; Sapar, L.

    2008-04-01

    Atutov and Shalagin (1988) proposed light-induced drift (LID) as a physically well understandable mechanism to explain the formation of isotopic anomalies observed in CP stars. We have generalized the theory of LID and applied it to diffusion of heavy elements and their isotopes in quiescent atmospheres of CP stars. Diffusional segregation of isotopes of chemical elements is described by the equations of continuity and diffusion velocity. Computations of evolutionary sequences for the abundances of mercury isotopes in several model atmospheres have been made, using the Fortran 90 program SMART composed by the authors. Results confirm predominant role of LID in separation of isotopes.

  9. Food-web dynamics and isotopic niches in deep-sea communities residing in a submarine canyon and on the adjacent open slopes

    USGS Publications Warehouse

    Demopoulos, Amanda W.J.; McClain-Counts, Jennifer; Ross, Steve W.; Brooke, Sandra; Mienis, Furu

    2017-01-01

    Examination of food webs and trophic niches provide insights into organisms' functional ecology, yet few studies have examined trophodynamics within submarine canyons, where the interaction of canyon morphology and oceanography influences habitat provision and food deposition. Using stable isotope analysis and Bayesian ellipses, we documented deep-sea food-web structure and trophic niches in Baltimore Canyon and the adjacent open slopes in the US Mid-Atlantic Region. Results revealed isotopically diverse feeding groups, comprising approximately 5 trophic levels. Regression analysis indicated that consumer isotope data are structured by habitat (canyon vs. slope), feeding group, and depth. Benthic feeders were enriched in 13C and 15N relative to suspension feeders, consistent with consuming older, more refractory organic matter. In contrast, canyon suspension feeders had the largest and more distinct isotopic niche, indicating they consume an isotopically discrete food source, possibly fresher organic material. The wider isotopic niche observed for canyon consumers indicated the presence of feeding specialists and generalists. High dispersion in δ13C values for canyon consumers suggests that the isotopic composition of particulate organic matter changes, which is linked to depositional dynamics, resulting in discrete zones of organic matter accumulation or resuspension. Heterogeneity in habitat and food availability likely enhances trophic diversity in canyons. Given their abundance in the world's oceans, our results from Baltimore Canyon suggest that submarine canyons may represent important havens for trophic diversity.

  10. Exploring the 13CO/C18O abundance ratio towards Galactic young stellar objects and HII regions

    NASA Astrophysics Data System (ADS)

    Areal, M. B.; Paron, S.; Celis Peña, M.; Ortega, M. E.

    2018-05-01

    Aims: Determining molecular abundance ratios is important not only for the study of Galactic chemistry, but also because they are useful to estimate physical parameters in a large variety of interstellar medium environments. One of the most important molecules for tracing the molecular gas in the interstellar medium is CO, and the 13CO/C18O abundance ratio is usually used to estimate molecular masses and densities of regions with moderate to high densities. Nowadays isotope ratios are in general indirectly derived from elemental abundances ratios. We present the first 13CO/C18O abundance ratio study performed from CO isotope observations towards a large sample of Galactic sources of different natures at different locations. Methods: To study the 13CO/C18O abundance ratio, we used 12CO J = 3 - 2 data obtained from the CO High-Resolution Survey, 13CO and C18O J = 3 - 2 data from the 13CO/C18O (J = 3 - 2) Heterodyne Inner Milky Way Plane Survey, and some complementary data extracted from the James Clerk Maxwell Telescope database. We analyzed a sample of 198 sources composed of young stellar objects (YSOs), and HII and diffuse HII regions as catalogued in the Red MSX Source Survey in 27.°5 ≤ l ≤ 46.°5 and |b|0.°5. Results: Most of the analyzed sources are located in the galactocentric distance range 4.0-6.5 kpc. We found that YSOs have, on average, lower 13CO/C18O abundance ratios than HII and diffuse HII regions. Taking into account that the gas associated with YSOs should be less affected by the radiation than in the case of the others sources, selective far-UV photodissociation of C18O is confirmed. The 13CO/C18O abundance ratios obtained in this work are systematically lower than those predicted from the known elemental abundance relations. These results will be useful in future studies of molecular gas related to YSOs and HII regions based on the observation of these isotopes.

  11. Forward Modeling of Carbonate Proxy Data from Planktonic Foraminifera using Oxygen Isotope Tracers in a Global Ocean Model

    NASA Technical Reports Server (NTRS)

    Schmidt, Gavin A.

    1999-01-01

    The distribution and variation of oxygen isotopes in seawater are calculated using the Goddard Institute for Space Studies global ocean model. Simple ecological models are used to estimate the planktonic foraminiferal abundance as a function of depth, column temperature, season, light intensity, and density stratification. These models are combined to forward model isotopic signals recorded in calcareous ocean sediment. The sensitivity of the results to the changes in foraminiferal ecology, secondary calcification, and dissolution are also examined. Simulated present-day isotopic values for ecology relevant for multiple species compare well with core-top data. Hindcasts of sea surface temperature and salinity are made from time series of the modeled carbonate isotope values as the model climate changes. Paleoclimatic inferences from these carbonate isotope records are strongly affected by erroneous assumptions concerning the covariations of temperature, salinity, and delta (sup 18)O(sub w). Habitat-imposed biases are less important, although errors due to temperature-dependent abundances can be significant.

  12. A Practical Cryogen-Free CO2 Purification and Freezing Technique for Stable Isotope Analysis.

    PubMed

    Sakai, Saburo; Matsuda, Shinichi

    2017-04-18

    Since isotopic analysis by mass spectrometry began in the early 1900s, sample gas for light-element isotopic measurements has been purified by the use of cryogens and vacuum-line systems. However, this conventional purification technique can achieve only certain temperatures that depend on the cryogens and can be sustained only as long as there is a continuous cryogen supply. Here, we demonstrate a practical cryogen-free CO 2 purification technique using an electrical operated cryocooler for stable isotope analysis. This approach is based on portable free-piston Stirling cooling technology and controls the temperature to an accuracy of 0.1 °C in a range from room temperature to -196 °C (liquid-nitrogen temperature). The lowest temperature can be achieved in as little as 10 min. We successfully purified CO 2 gas generated by carbonates and phosphoric acid reaction and found its sublimation point to be -155.6 °C at 0.1 Torr in the vacuum line. This means that the temperature required for CO 2 trapping is much higher than the liquid-nitrogen temperature. Our portable cooling system offers the ability to be free from the inconvenience of cryogen use for stable isotope analysis. It also offers a new cooling method applicable to a number of fields that use gas measurements.

  13. Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

    NASA Technical Reports Server (NTRS)

    Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C.-Y.; Fujitani, T.; Okano, O.

    2011-01-01

    Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

  14. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  15. Mantle rare gas relative abundances in a steady-state mass transport model

    NASA Technical Reports Server (NTRS)

    Porcelli, D.; Wasserburg, G. J.

    1994-01-01

    A model for He and Xe was presented previously which incorporates mass transfer of rare gases from an undegassed lower mantle (P) and the atmosphere into a degassed upper mantle (D). We extend the model to include Ne and Ar. Model constraints on rare gas relative abundances within P are derived. Discussions of terrestrial volatile acquisition have focused on the rare gas abundance pattern of the atmosphere relative to meteoritic components, and the pattern of rare gases still trapped in the Ear,th is important in identifying volatile capture and loss processes operating during Earth formation. The assumptions and principles of the model are discussed in Wasserburg and Porcelli (this volume). For P, the concentrations in P of the decay/nuclear products 4 He, 21 Ne, 40 Ar, and 136 Xe can be calculated from the concentrations of the parent elements U, Th, K, and Pu. The total concentration of the daughter element in P is proportional to the isotopic shifts in P. For Ar, ((40)Ar/(36)Ar)p - ((40)Ar/(36)Ar)o =Delta (exp 40) p= 40 Cp/(exp 36)C where(i)C(sub j) the concentration of isotope i in j. In D, isotope compositions are the result of mixing rare gases from P, decay/nuclear products generated in the upper mantle, and subducted rare gases (for Ar and Xe).

  16. Image segmentation for uranium isotopic analysis by SIMS: Combined adaptive thresholding and marker controlled watershed approach

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

    Willingham, David G.; Naes, Benjamin E.; Heasler, Patrick G.

    A novel approach to particle identification and particle isotope ratio determination has been developed for nuclear safeguard applications. This particle search approach combines an adaptive thresholding algorithm and marker-controlled watershed segmentation (MCWS) transform, which improves the secondary ion mass spectrometry (SIMS) isotopic analysis of uranium containing particle populations for nuclear safeguards applications. The Niblack assisted MCWS approach (a.k.a. SEEKER) developed for this work has improved the identification of isotopically unique uranium particles under conditions that have historically presented significant challenges for SIMS image data processing techniques. Particles obtained from five NIST uranium certified reference materials (CRM U129A, U015, U150, U500more » and U850) were successfully identified in regions of SIMS image data 1) where a high variability in image intensity existed, 2) where particles were touching or were in close proximity to one another and/or 3) where the magnitude of ion signal for a given region was count limited. Analysis of the isotopic distributions of uranium containing particles identified by SEEKER showed four distinct, accurately identified 235U enrichment distributions, corresponding to the NIST certified 235U/238U isotope ratios for CRM U129A/U015 (not statistically differentiated), U150, U500 and U850. Additionally, comparison of the minor uranium isotope (234U, 235U and 236U) atom percent values verified that, even in the absence of high precision isotope ratio measurements, SEEKER could be used to segment isotopically unique uranium particles from SIMS image data. Although demonstrated specifically for SIMS analysis of uranium containing particles for nuclear safeguards, SEEKER has application in addressing a broad set of image processing challenges.« less

  17. 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

  18. DeuteRater: a tool for quantifying peptide isotope precision and kinetic proteomics.

    PubMed

    Naylor, Bradley C; Porter, Michael T; Wilson, Elise; Herring, Adam; Lofthouse, Spencer; Hannemann, Austin; Piccolo, Stephen R; Rockwood, Alan L; Price, John C

    2017-05-15

    Using mass spectrometry to measure the concentration and turnover of the individual proteins in a proteome, enables the calculation of individual synthesis and degradation rates for each protein. Software to analyze concentration is readily available, but software to analyze turnover is lacking. Data analysis workflows typically don't access the full breadth of information about instrument precision and accuracy that is present in each peptide isotopic envelope measurement. This method utilizes both isotope distribution and changes in neutromer spacing, which benefits the analysis of both concentration and turnover. We have developed a data analysis tool, DeuteRater, to measure protein turnover from metabolic D 2 O labeling. DeuteRater uses theoretical predictions for label-dependent change in isotope abundance and inter-peak (neutromer) spacing within the isotope envelope to calculate protein turnover rate. We have also used these metrics to evaluate the accuracy and precision of peptide measurements and thereby determined the optimal data acquisition parameters of different instruments, as well as the effect of data processing steps. We show that these combined measurements can be used to remove noise and increase confidence in the protein turnover measurement for each protein. Source code and ReadMe for Python 2 and 3 versions of DeuteRater are available at https://github.com/JC-Price/DeuteRater . Data is at https://chorusproject.org/pages/index.html project number 1147. Critical Intermediate calculation files provided as Tables S3 and S4. Software has only been tested on Windows machines. jcprice@chem.byu.edu. Supplementary data are available at Bioinformatics online. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com

  19. Magnesium Isotope Ratios in ω Centauri Red Giants

    NASA Astrophysics Data System (ADS)

    Da Costa, G. S.; Norris, John E.; Yong, David

    2013-05-01

    We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R ~ 100,000) and at Gemini-S with b-HROS (R ~ 150,000) to determine magnesium isotope ratios for seven ω Cen red giants that cover a range in iron abundance from [Fe/H] = -1.78 to -0.78 dex, and for two red giants in M4 (NGC 6121). The ω Cen stars sample both the "primordial" (i.e., O-rich, Na- and Al-poor) and the "extreme" (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both ω Cen and M4 show (25Mg, 26Mg)/24Mg isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the ω Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the 26Mg/24Mg ratio is highest at intermediate metallicities ([Fe/H] < -1.4 dex), and for the highest [Al/Fe] values. Further, the relative abundance of 26Mg in the extreme population stars is notably higher than that of 25Mg, in contrast to model predictions. The 25Mg/24Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.

  20. Doppler Imaging and Chemical Abundance Analysis of EK Dra: Capabilities of Small Telescopes

    NASA Astrophysics Data System (ADS)

    Kilicoglu, Tolgahan; Senavci, H. V.; Bahar, E.; Isik, E.; Montes, D.; Hussain, G. A. J.

    2018-04-01

    We investigate the chromospheric and spot activity behaviour of the young Solar-like star EK Dra via Doppler imaging and spectral synthesis methods, using mid-resolution time series spectra of the system. We also present the atmospheric parameters and detailed elemental photospheric abundances of the star. The chemical abundance pattern of EK Dra do not suggest any remarkable peculiarities except few elements. The Titanium Oxide (TiO) bandheads at 7000 - 7100 A region also give clues about the spot temperature that may be cooler than 4000 K. In addition, we also discuss the capabilities of small telescopes (40 cm in our case) and medium resolution spectrographs in terms of Doppler imaging and chemical abundance analysis.

  1. Iron physiological requirements in Chinese adults assessed by the stable isotope labeling technique.

    PubMed

    Cai, Jie; Ren, Tongxiang; Zhang, Yuhui; Wang, Zhilin; Gou, Lingyan; Huang, Zhengwu; Wang, Jun; Piao, Jianhua; Yang, Xiaoguang; Yang, Lichen

    2018-01-01

    Iron is a kind of essential trace mineral in the human body, while the studies on its physiological requirement are very limited recently, especially in China. And most studies were performed with the radioisotope tracer technique, which was harmful to health. This study aimed to first get the value of iron physiological requirements in Chinese adults assessed by the stable isotope labeling technique. Forty-four eligible young Chinese healthy adults were randomly recruited from the Bethune Military Medical College (Shijiazhuang, Hebei, China) between January 2010 and March 2011, and 19 subjects were included in the final data analysis. After adaptive diets and observation, subjects received 58 Fe intravenously. The baseline venous blood sample and general information were collected on day 0. Venous blood samples were also collected on day 14, 30, 60, 100, 120, 150, 240, 330, 425, 515, 605, 767, 1155, respectively. The blood samples were acid digested by a Microwave Digestion System and then analyzed by the MC-ICP-MS and Atomic Absorption Spectroscopy to get the abundance of Fe isotopes and the total iron concentration respectively. The circulation rate (the proportion of blood iron to whole body iron) could be calculated by the intake amount, background content and the peak isotope content. When the abundance changed stably, the iron physiological requirement could be calculated by the iron loss in a period of time. The abundance of 58 Fe reached its peak on day 14, and changed stably from day 425. The average circulation rate was 84%, with no significance difference between the 2 genders. The mean iron requirement in females was 1101.68 μg/d, and the mean requirement adjusted by body weight was 20.69 μg/kg.d. For males, the mean iron requirement was 959.9 μg/d, and the requirement adjusted by body weight was 14.04 μg/kg.d. Our study has obtained the data about the iron physiological requirements of Chinese adults using stable isotope labeling technique

  2. Isotopic Dichotomy among Meteorites and Its Bearing on the Protoplanetary Disk

    NASA Astrophysics Data System (ADS)

    Scott, Edward R. D.; Krot, Alexander N.; Sanders, Ian S.

    2018-02-01

    Whole rock Δ17O and nucleosynthetic isotopic variations for chromium, titanium, nickel, and molybdenum in meteorites define two isotopically distinct populations: carbonaceous chondrites (CCs) and some achondrites, pallasites, and irons in one and all other chondrites and differentiated meteorites in the other. Since differentiated bodies accreted 1–3 Myr before the chondrites, the isotopic dichotomy cannot be attributed to temporal variations in the disk. Instead, the two populations were most likely separated in space, plausibly by proto-Jupiter. Formation of CCs outside Jupiter could account for their characteristic chemical and isotopic composition. The abundance of refractory inclusions in CCs can be explained if they were ejected by disk winds from near the Sun to the disk periphery where they spiraled inward due to gas drag. Once proto-Jupiter reached 10–20 M ⊕, its external pressure bump could have prevented millimeter- and centimeter-sized particles from reaching the inner disk. This scenario would account for the enrichment in CCs of refractory inclusions, refractory elements, and water. Chondrules in CCs show wide ranges in Δ17O as they formed in the presence of abundant 16O-rich refractory grains and 16O-poor ice particles. Chondrules in other chondrites (ordinary, E, R, and K groups) show relatively uniform, near-zero Δ17O values as refractory inclusions and ice were much less abundant in the inner solar system. The two populations were plausibly mixed together by the Grand Tack when Jupiter and Saturn migrated inward emptying and then repopulating the asteroid belt with roughly equal masses of planetesimals from inside and outside Jupiter’s orbit (S- and C-type asteroids).

  3. New isotopic clues to solar system formation

    NASA Technical Reports Server (NTRS)

    Lee, T.

    1979-01-01

    The presence of two new extinct nuclides Al-26 and Pd-107 with half lives of approximately one million years in the early solar system implies that there were nucleosynthetic activities involving a great many elements almost at the instant of solar system formation. Rate gas and oxygen isotopic abundance variations ('anomalies') relative to the 'cosmic' composition were observed in a variety of planetary objects, which indicates that isotopic heterogeneities caused by the incomplete mixing of distinct nucleosynthesis components permeate the entire solar system. These new results have major implications for cosmochronology, nucleosynthesis theory, star formation, planetary heating, and the genetic relationship between different planetary bodies

  4. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  5. Stardust from Supernovae and Its Isotopes

    NASA Astrophysics Data System (ADS)

    Hoppe, Peter

    Primitive solar system materials, namely, meteorites, interplanetary dust particles, and cometary matter contain small quantities of nanometer- to micrometer-sized refractory dust grains that exhibit large isotopic abundance anomalies. These grains are older than our solar system and have been named "presolar grains." They formed in the winds of red giant and asymptotic giant stars and in the ejecta of stellar explosions, i.e., represent a sample of stardust that can be analyzed in terrestrial laboratories for isotopic compositions and other properties. The inventory of presolar grains is dominated by grains from red giant and asymptotic giant branch stars. Presolar grains from supernovae form a minor but important subpopulation. Supernova (SN) minerals identified to date include silicon carbide, graphite, silicon nitride, oxides, and silicates. Isotopic studies of major, minor, and trace elements in these dust grains have provided detailed insights into nucleosynthetic and mixing processes in supernovae and how dust forms in these violent environments.

  6. Oxygen isotopes and the moon-forming giant impact.

    PubMed

    Wiechert, U; Halliday, A N; Lee, D C; Snyder, G A; Taylor, L A; Rumble, D

    2001-10-12

    We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

  7. Isotopic 13C NMR spectrometry to assess counterfeiting of active pharmaceutical ingredients: site-specific 13C content of aspirin and paracetamol.

    PubMed

    Silvestre, Virginie; Mboula, Vanessa Maroga; Jouitteau, Catherine; Akoka, Serge; Robins, Richard J; Remaud, Gérald S

    2009-10-15

    Isotope profiling is a well-established technique to obtain information about the chemical history of a given compound. However, the current methodology using IRMS can only determine the global (13)C content, leading to the loss of much valuable data. The development of quantitative isotopic (13)C NMR spectrometry at natural abundance enables the measurement of the (13)C content of each carbon within a molecule, thus giving simultaneous access to a number of isotopic parameters. When it is applied to active pharmaceutical ingredients, each manufactured batch can be characterized better than by IRMS. Here, quantitative isotopic (13)C NMR is shown to be a very promising and effective tool for assessing the counterfeiting of medicines, as exemplified by an analysis of aspirin (acetylsalicylic acid) and paracetamol (acetaminophen) samples collected from pharmacies in different countries. It is proposed as an essential complement to (2)H NMR and IRMS.

  8. Wildfire Activity Across the Triassic-Jurassic Boundary in the Polish Basin: Evidence from New Fossil Charcoal & Carbon-isotope Data

    NASA Astrophysics Data System (ADS)

    Pointer, R.; Belcher, C.; Hesselbo, S. P.; Hodbod, M.; Pieńkowski, G.

    2017-12-01

    New fossil charcoal abundance and carbon-isotope data from two sedimentary cores provide new evidence of extreme environmental conditions in the Polish Basin during the Latest Triassic to Earliest Jurassic. Sedimentary cores from the Polish Basin provide an excellent record of terrestrial environmental conditions across the Triassic-Jurassic Boundary, a time of climatic extremes. Previous work has shown that the marine realm was affected by a large perturbation to the carbon cycle across the Triassic-Jurassic Boundary (manifested by large negative and positive carbon-isotope excursions) and limited records of charcoal abundance and organic geochemistry have indicated important changes in fire regime in the coeval ecosystems. Here we present two new carbon-isotope records generated from fossil plant matter across the Triassic-Jurassic boundary, and present new charcoal records. The charcoal abundance data confirm that there was variation in wildfire activity during the Late Triassic-Early Jurassic in the Polish Basin. Peaks in the number of fossil charcoal fragments present occur in both sedimentary cores, and increases in fossil charcoal abundance are linked to wildfires, signalling a short-lived rise in wildfire activity. Fossil charcoal abundance does not appear to be fully controlled by total organic matter content, depositional environment or bioturbation. We argue that increased wildfire activity is likely caused by an increase in ignition of plant material as a result of an elevated number of lightning strikes. Global warming (caused by a massive input of carbon into the atmosphere, as indicated by carbon-isotope data) can increase storm activity, leading to increased numbers of lightning strikes. Previous Triassic-Jurassic Boundary wildfire studies have found fossil charcoal abundance peaks at other northern hemisphere sites (Denmark & Greenland), and concluded that they represent increases in wildfire activity in the earliest Jurassic. Our new charcoal and

  9. 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.

  10. Chronology of chrondrule and CAI formation: Mg-Al isotopic evidence

    NASA Technical Reports Server (NTRS)

    Macpherson, G. J.; Davis, A. M.

    1994-01-01

    Details of the chondrule and Ca-Al-rich inclusion (CAI) formation during the earliest history of the solar system are imperfectly known. Because CAI's are more 'refractory' than ferromagnesian chondrules and have the lowest recorded initial Sr-87/Sr-86 ratios of any solar system materials, the expectation is that CAI's formed earlier than chondrules. But it is not known, for example, if CAI formation had stopped by the time chondrule formation began. Conventional (absolute) age-dating techniques cannot adequately resolve small age differences (less than 10(exp 6) years) between objects of such antiquity. One approach has been to look at systematic differences in the daughter products of short-lived radionuclides such as Al-26 and I-129. Unfortunately, neither system appears to be 'well-behaved.' One possible reason for this circumstance is that later secondary events have partially reset the isotopic systems, but a viable alternative continues to be large-scale (nebular) heterogeneity in initial isotopic abundances, which would of course render the systems nearly useless as chronometers. In the past two years the nature of this problem has been redefined somewhat. Examination of the Al-Mg isotopic database for all CAI's suggests that the vast majority of inclusions originally had the same initial Al-26/Al-27 abundance ratio, and that the ill-behaved isotopic systematics now observed are the results of later partial reequilibration due to thermal processing. Isotopic heterogeneities did exist in the nebula, as demonstrated by the existence of so-called FUN inclusions in CV3 chondrites and isotopically anomalous hibonite grains in CM2 chondrites, which had little or no live Al-26 at the time of their formation. But, among the population of CV3 inclusions at least, FUN inclusions appear to have been a relatively minor nebular component.

  11. Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

    NASA Astrophysics Data System (ADS)

    Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

    2014-12-01

    Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

  12. Isotope Analysis Reveals Foraging Area Dichotomy for Atlantic Leatherback Turtles

    PubMed Central

    Angulo, Elena; Das, Krishna; Girondot, Marc

    2008-01-01

    Background The leatherback turtle (Dermochelys coriacea) has undergone a dramatic decline over the last 25 years, and this is believed to be primarily the result of mortality associated with fisheries bycatch followed by egg and nesting female harvest. Atlantic leatherback turtles undertake long migrations across ocean basins from subtropical and tropical nesting beaches to productive frontal areas. Migration between two nesting seasons can last 2 or 3 years, a time period termed the remigration interval (RI). Recent satellite transmitter data revealed that Atlantic leatherbacks follow two major dispersion patterns after nesting season, through the North Gulf Stream area or more eastward across the North Equatorial Current. However, information on the whole RI is lacking, precluding the accurate identification of feeding areas where conservation measures may need to be applied. Methodology/Principal Findings Using stable isotopes as dietary tracers we determined the characteristics of feeding grounds of leatherback females nesting in French Guiana. During migration, 3-year RI females differed from 2-year RI females in their isotope values, implying differences in their choice of feeding habitats (offshore vs. more coastal) and foraging latitude (North Atlantic vs. West African coasts, respectively). Egg-yolk and blood isotope values are correlated in nesting females, indicating that egg analysis is a useful tool for assessing isotope values in these turtles, including adults when not available. Conclusions/Significance Our results complement previous data on turtle movements during the first year following the nesting season, integrating the diet consumed during the year before nesting. We suggest that the French Guiana leatherback population segregates into two distinct isotopic groupings, and highlight the urgent need to determine the feeding habitats of the turtle in the Atlantic in order to protect this species from incidental take by commercial fisheries. Our

  13. Enhanced spatially-resolved trace analysis using combined SIMS-single-stage AMS

    NASA Astrophysics Data System (ADS)

    Grabowski, K. S.; Groopman, E. E.; Fahey, A. J.

    2017-11-01

    Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20-50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

  14. Elemental and Isotopic Analysis of Uranium Oxide an NIST Glass Standards by FEMTOSECOND-LA-ICP-MIC-MS

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

    Ebert, Chris; Zamzow, Daniel S.; McBay, Eddie H.

    2009-06-01

    The objective of this work was to test and demonstrate the analytical figures of merit of a femtosecond-laser ablation (fs-LA) system coupled with an inductively coupled plasma-multi-ion collector-mass spectrometer (ICP-MIC-MS). The mobile fs-LA sampling system was designed and assembled at Ames Laboratory and shipped to Oak Ridge National Laboratory (ORNL), where it was integrated with an ICP-MIC-MS. The test period of the integrated systems was February 2-6, 2009. Spatially-resolved analysis of particulate samples is accomplished by 100-shot laser ablation using a fs-pulsewidth laser and monitoring selected isotopes in the resulting ICP-MS transient signal. The capability of performing high sensitivity, spatiallymore » resolved, isotopic analyses with high accuracy and precision and with virtually no sample preparation makes fs-LA-ICP-MIC-MS valuable for the measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. Femtosecond-LA has been shown to generate particles from the sample that are more representative of the bulk composition, thereby minimizing weaknesses encountered in previous work using nanosecond-LA (ns-LA). The improvement of fs- over ns-LA sampling arises from the different mechanisms for transfer of energy into the sample in these two laser pulse-length regimes. The shorter duration fs-LA pulses induce less heating and cause less damage to the sample than the longer ns pulses. This results in better stoichiometric sampling (i.e., a closer correlation between the composition of the ablated particles and that of the original solid sample), which improves accuracy for both intra- and inter-elemental analysis. The primary samples analyzed in this work are (a) solid uranium oxide powdered samples having different {sup 235}U to {sup 238}U concentration ratios, and (b) glass reference materials (NIST 610, 612, 614, and 616). Solid uranium oxide samples containing {sup 235}U in depleted, natural, and

  15. A guide for the laboratory information management system (LIMS) for light stable isotopes--Versions 7 and 8

    USGS Publications Warehouse

    Coplen, Tyler B.

    2000-01-01

    data based on the time of day of analysis. Whereas Finnigan ISODAT software is confined to using only a single peak for calculating delta values, LIMS now enables one to use the mean of two or more reference injections during a continuous flow analysis to calculate delta values. This is useful with Finnigan?s GasBench II online sample preparation system. Concentrations of carbon, nitrogen, and sulfur can be calculated based one or more isotopic reference materials analyzed with a group of samples. Both sample data and isotopic analysis data can now be exported to Excel files. A calculator for determining the amount of sample needed for isotopic analysis based on a previous amount of sample and continuous flow area is now an integral part of LIMS for Light Stable Isotopes. LIMS for Light Stable Isotopes can now assign an error code to Finnigan elemental analyzer analyses in which one of the electrometers has saturated due to analysis of too much sample material, giving rise to incorrect isotopic abundances. Information on downloading this report and downloading code and databases is provided at the Internet addresses: http://water.usgs.gov/software/geochemical.html or http://www.geogr.uni-jena.de/software/geochemical.html in the Eastern Hemisphere.

  16. Following Carbon Isotopes from Methane to Molecules

    NASA Astrophysics Data System (ADS)

    Freeman, K. H.

    2017-12-01

    Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

  17. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

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

    Magdas, D. A., E-mail: gabriela.cristea@itim-cj.ro; Cristea, G., E-mail: gabriela.cristea@itim-cj.ro; Bot, A.

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ{sup 18}O and δ{sup 2}H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also verymore » important: in summer, milk water contains higher δ{sup 18}O and δ{sup 2}H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.« less

  18. Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

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

    Schoeller, D.A.; Leitch, C.A.; Brown, C.

    The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO/sub 2/ excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37/sup 0/C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water,more » local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O/sub 2/ and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO/sub 2/ production.« less

  19. Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

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

    Finkelstein, Myra E., E-mail: myraf@ucsc.edu; Kuspa, Zeka E.; Welch, Alacia

    Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot frommore » all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.« less

  20. A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon and nitrogen. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Zumberge, J. F.

    1981-01-01

    The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen were measured at energies near 300 MeV amu, using a balloon-borne instrument at an atmospheric depth of approximately 5 g/sq cm. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintillators used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from approximately 0.3 amu at boron to approximately 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere the results are B-10/B=0.33 (+0.17, -0.11), C-13/C=0.06 (+0.13, -0.11), and N-15/N=0.42 (+0.19, -0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near Earth consistent with the measurements.

  1. Using Stable Isotopes to Assess Connectivity: the Importance of Oceanic and Watershed Nitrogen Sources for Estuarine Primary Producers

    EPA Science Inventory

    Estuaries located at the interface of terrestrial and oceanic ecosystems receive nutrients from both ecosystems. Stable isotopes of primary producers and consumers are often used as an indicator of nutrient sources. We assembled natural abundance nitrogen stable isotope (δ15N) d...

  2. Biodegradation of Chlorofluorocarbons in a Groundwater Plume using Compound Specific Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Phillips, E.; Manna, J.; Horst, A.; Gilevska, T.; Sherwood Lollar, B.; Mack, E. E.; Seger, E.; Lutz, E. J.; Norcoss, S.; Morgan, S. E.; West, K. A.; Dworatzek, S.; Webb, J.

    2017-12-01

    Compound specific isotope analysis (CSIA) measures isotope ratios of organic hydrocarbons to monitor intrinsic bioremediation processes that can transform contaminants in field settings. The fraction of original contaminant remaining can be determined using the measured isotope ratio of the contaminant by an experimentally determined fractionation factor. In this study, two separate biotransformation experiments were performed in the Stable Isotope Laboratory at the University of Toronto using CSIA. In these two experiments, a mixed culture derived from a contaminated site was amended with trichlorotrifluoroethane (CFC-113), or trichlorofluoromethane (CFC-11), respectively. The concentrations and carbon isotope ratios of CFC-113, or CFC-11 were analyzed to calculate the fractionation factor for the transformation of each compound. Subsequently, groundwater samples from 9 wells at a historically contaminated site were collected and analyzed. The experimentally determined fractionation factors were then used to evaluate the extent of transformation that had occurred at the field site. In the laboratory studies, significant carbon isotope fractionation was observed for both CFC-113 and CFC-11 as biotransformation proceeded. This significant fractionation is beneficial when evaluating biotransformation at field sites as it can be clearly differentiated from the effects of other physical processes such as transport, or volatilization. Although there was significant variation in the carbon isotope values of CFC-113 between different well locations at the field site, these variations may be due to differences in source carbon isotope signatures. For CFC-11, much more significant isotopic variation was observed within the same well and between wells, showing trends consistent with in situ biotransformation. Results from this study demonstrate that CSIA can be successfully applied to evaluate the extent of transformation of chlorofluorocarbons (CFCs) at contaminated field

  3. Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Niemann, Hasso (Technical Monitor)

    2001-01-01

    Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

  4. Oxygen isotopic ratios of primordial water in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru

    2018-01-01

    In this work, I estimate the δ18 O and δ17 O values of primordial water in CM chondrites to be 55 ± 13 and 35 ± 9‰, respectively, based on whole-rock O and H data. Also, I found that the O and/or H data of Antarctic meteorites are biased, which is attributed to terrestrial weathering. This characteristic O isotopic ratio of water together with corresponding water abundances in CM chondrites are consistent with the origin of water as ice processed by photochemical reactions at the outer regions of the solar nebula, where mass-independent O isotopic fractionation and water destruction may have occurred. Another possible mechanism to produce the inferred O isotopic ratio of water would be O isotopic fractionation between water vapor and ice, which likely occurred near the condensation front of H2O (snow line) in the solar nebula. The inferred O isotopic ratio of water suggests that carbonate in CM chondrites formed at low temperatures of <150 °C. The O isotopic ratios of primordial water in chondrites other than CM chondrites are not well constrained.

  5. Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2009-01-01

    NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here. we present the carbon isotopic ratios of glycine and E-aminocaproic acid (EACH), the two most abundant amino acids observed, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio crass spectrometry coupled with quadrupole mass spectrometry (GC-QMS/IRMS).

  6. Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie

    2009-01-01

    NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here, we present the carbon isotopic ratios of glycine and e-aminocaproic acid (EACA), the two most abundant amino acids, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio mass spectrometry coupled with quadrupole mass spectrometry (GC-CAMS/IRMS).

  7. The Abundance and Isotopic Composition of Water in Howardite-Eucrite-Diogenite Meteorites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Tartèse, R.; Anand, M.; Franchi, I. A.; Grady, M. M.; Greenwood, R. C.; Charlier, B. L. A.

    2014-09-01

    Using SIMs techniques we measure OH abundances and D/H ratios in apatite grains from two Eucrites (DaG 945, DaG 844).The average δD values of these two samples are also similar to carbonaceous chondrites, the Earth and the Moon.

  8. Determining the source of house flies (Musca domestica) using stable isotope analysis.

    PubMed

    Heinrich, Katharina; Weaver, Robert J; Bell, Howard A

    2012-01-01

    Intensive livestock units frequently produce flies in large numbers that, on migration, cause nuisance to the occupants of neighbouring dwellings. The resolution of such problems is often reliant on the unequivocal identification of the origin of the flies, particularly when several potential sources exist. This study evaluated stable isotope analysis as a method for differentiating adult houseflies (Musca domestica) on the basis of their dietary history so as to determine their likely source. Flies were reared in the laboratory on several substrates, including chicken and cattle manure, laboratory diet and household vegetable waste. Different fly parts (wings, heads and legs) and whole flies were analysed immediately after eclosion and after 10 days. The δ(13) C and δ(15) N values for adults that had developed on each diet type were highly distinct. Both isotopic ratios altered markedly after maintaining the flies for 10 days on a diet of cane sugar solution. Stable isotope analysis readily differentiated flies that had developed on a range of substrates. The technique, therefore, shows potential to be employed to determine the likely source of various nuisance insects, and to contribute to the abatement of such problems. Copyright © 2011 Society of Chemical Industry.

  9. On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

    NASA Astrophysics Data System (ADS)

    Bauska, T.; Hodell, D. A.; Walters, G.

    2016-12-01

    Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

  10. 2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  11. High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

    Wall, Andrew J.; Capo, Rosemary C.; Stewart, Brian W.

    2016-09-22

    This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

  12. High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

    Hakala, Jacqueline Alexandra

    2016-11-22

    This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

  13. Origin of the eclogitic clasts with graphite-bearing and graphite-free lithologies in the Northwest Africa 801 (CR2) chondrite: Possible origin from a Moon-sized planetary body inferred from chemistry, oxygen isotopes and REE abundances

    NASA Astrophysics Data System (ADS)

    Hiyagon, H.; Sugiura, N.; Kita, N. T.; Kimura, M.; Morishita, Y.; Takehana, Y.

    2016-08-01

    In order to clarify the origin of the eclogitic clasts found in the NWA801 (CR2) chondrite (Kimura et al., 2013), especially, that of the high pressure and temperature (P-T) condition (∼3 GPa and ∼1000 °C), we conducted ion microprobe analyses of oxygen isotopes and rare earth element (REE) abundances in the clasts. Oxygen isotopic compositions of the graphite-bearing lithology (GBL) and graphite-free lithology (GFL) show a slope ∼0.6 correlation slightly below the CR-CH-CB chondrites field in the O three-isotope-diagram, with a large variation for the former and almost homogeneous composition for the latter. The average REE abundances of the two lithologies show almost unfractionated patterns. Based on these newly obtained data, as well as mineralogical observations, bulk chemistry, and considerations about diffusion timescales for various elements, we discuss in detail the formation history of the clasts. Consistency of the geothermobarometers used by Kimura et al. (2013), suggesting equilibration of various elements among different mineral pairs, provides a strong constraint for the duration of the high P-T condition. We suggest that the high P-T condition lasted 102-103 years. This clearly precludes a shock high pressure (HP) model, and hence, strongly supports a static HP model. A static HP model requires a Moon-sized planetary body of ∼1500 km in radius. Furthermore, it implies two successive violent collisions, first at the formation of the large planetary body, when the clasts were placed its deep interior, and second, at the disruption of the large planetary body, when the clasts were expelled out of the parent body and later on transported to the accretion region of the CR chondrites. We also discuss possible origin of O isotopic variations in GBL, and presence/absence of graphite in GBL/GFL, respectively, in relation to smelting possibly occurred during the igneous process(es) which formed the two lithologies. Finally we present a possible

  14. 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.

  15. Contribution of bulk mass spectrometry isotopic analysis to characterization of materials in the framework of CMX-4

    DOE PAGES

    Kuchkin, A.; Stebelkov, V.; Zhizhin, K.; ...

    2018-01-30

    Seven laboratories used the results of bulk uranium isotopic analysis by either inductively coupled plasma mass spectrometry (ICP-MS) or thermal ionization mass spectrometry (TIMS) for characterization of the samples in the Nuclear Forensic International Technical Working Group fourth international collaborative material exercise, CMX-4. Comparison of the measured isotopic compositions of uranium in three exercise samples is implemented for identifying any differences or similarities between the samples. The role of isotopic analyses in the context of a real nuclear forensic investigation is discussed. Several limitations in carrying out ICP-MS or TIMS analysis in CMX-4 are noted.

  16. Contribution of bulk mass spectrometry isotopic analysis to characterization of materials in the framework of CMX-4

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

    Kuchkin, A.; Stebelkov, V.; Zhizhin, K.

    Seven laboratories used the results of bulk uranium isotopic analysis by either inductively coupled plasma mass spectrometry (ICP-MS) or thermal ionization mass spectrometry (TIMS) for characterization of the samples in the Nuclear Forensic International Technical Working Group fourth international collaborative material exercise, CMX-4. Comparison of the measured isotopic compositions of uranium in three exercise samples is implemented for identifying any differences or similarities between the samples. The role of isotopic analyses in the context of a real nuclear forensic investigation is discussed. Several limitations in carrying out ICP-MS or TIMS analysis in CMX-4 are noted.

  17. Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

    USGS Publications Warehouse

    Böhlke, J.K.; Smith, R.L.; Hannon, J.E.

    2007-01-01

    Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible δ15N and δ18O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ15N and ±0.4−1.0‰ for δ18O) and moderately enriched 15N tracer levels (±20−50‰ for δ15N near 5000‰) for 5−20 nmol of NO2- (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO2-and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

  18. Hydrogen Isotope Geochemistry of Mariana Trough Lavas

    NASA Astrophysics Data System (ADS)

    Oleary, J.; Kitchen, N.; Eiler, J.

    2002-12-01

    Basaltic lavas from the Marianas trough vary in water content from values similar to mid-ocean ridge basalts (MORBs) to ten times those values. These variations plausibly reflect addition of subducted water to the mantle wedge, but must also reflect variations in extent of melting and crystallization-differentiation. We report hydrogen isotope data for 18 samples of lavas from the Mariana trough; these measurements, when combined with other geochemical data, constrain the relative proportions of subducted vs. 'primitive' water in their mantle sources. Previous measurements of the hydrogen isotope composition of Mariana trough lavas [1] found a correlation between dD and measured water content, consistent with two-component mixing between water in the ambient MORB source and water from the subducted slab, but include only four samples, only two of which have known major and minor element geochemistry. Our purpose is to confirm this result and expand it to include a more representative sampling. Our measurements made use of a recently developed technique for on-line stepped heating, water reduction and hydrogen isotope mass spectrometry [2]. This method is appropriate for relatively small samples of basaltic glass (ca. 100 μg to 1 mg) and up to 10 analyses can be performed per day. Its principle advantages for our purposes are that it can be applied to even small or glass-poor samples and it is fast enough to permit replication of all data and analysis of relatively large numbers of standards. Hydrogen isotope compositions of Mariana trough lavas vary between -74 per mil and -34 per mil (SMOW); this compares with a range of -46 to -32 per mil for related lavas in [1] and is similar to the previously observed range for back-arc-basin basalts generally (-70 to -32 per mil). Two-thirds of our sample suite span a small range in dD (-40+/-4 ). We suggest this average is the most representative value for back arc basin basalts measured to-date. Our data are inconsistent

  19. Pb isotope compositions of modern deep sea turbidites

    NASA Astrophysics Data System (ADS)

    Hemming, S. R.; McLennan, S. M.

    2001-01-01

    Modern deep sea turbidite muds and sands collected from Lamont piston cores represent a large range in age of detrital sources as well as a spectrum of tectonic settings. Pb isotope compositions of all but three of the 66 samples lie to the right of the 4.56 Ga Geochron, and most also lie along a slope consistent with a time-integrated κ ( 232Th/ 238U) between 3.8 and 4.2. Modern deep sea turbidites show a predictable negative correlation between both Pb and Sr isotope ratios and ɛNd and ɛHf, clearly related to the age of continental sources. However, the consistency between Pb and Nd isotopes breaks down for samples with very old provenance ( ɛNd<-20) that are far less radiogenic than predicted by the negative correlation. The correlations among Sr, Nd and Hf isotopes also become more scattered in samples with very old provenance. The unradiogenic Pb isotopic character of modern sediments with Archean Nd model ages is consistent with a model where Th and U abundances of the Archean upper crust are significantly lower than the post-Archean upper crust.

  20. Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

    NASA Astrophysics Data System (ADS)

    Bean, J. R.; Hill, T. M.; Guerra, C.

    2007-12-01

    The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

  1. Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Pizzarello, Sandra; Huang, Yongsong

    2002-05-01

    The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI- and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three through ten-carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of forty-four of these compounds were detected with the most abundant, succinic acid, present at ~40 nmoles/g. met. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound to compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All delta D and delta 13C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. Delta D values vary from, approximately, + 1120 deg for succinic acid to + 1530 deg for methyl glutaric acid. Delta 13C values ranged from + 12.6 deg for methyl glutaric acid to + 22.9 deg for glutaric acid, with adipic acid having a significantly lower value (+ 5.5 deg). Murchison dicarboxylic acid showed similar isotopic values: their delta 13C values were generally

  2. MAGNESIUM ISOTOPE RATIOS IN {omega} CENTAURI RED GIANTS

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

    Da Costa, G. S.; Norris, John E.; Yong, David

    2013-05-20

    We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R {approx} 100,000) and at Gemini-S with b-HROS (R {approx} 150,000) to determine magnesium isotope ratios for seven {omega} Cen red giants that cover a range in iron abundance from [Fe/H] = -1.78 to -0.78 dex, and for two red giants in M4 (NGC 6121). The {omega} Cen stars sample both the ''primordial'' (i.e., O-rich, Na- and Al-poor) and the ''extreme'' (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both {omega} Cen and M4 show ({sup 25}Mg, {sup 26}Mg)/{sup 24}Mgmore » isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the {omega} Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the {sup 26}Mg/{sup 24}Mg ratio is highest at intermediate metallicities ([Fe/H] < -1.4 dex), and for the highest [Al/Fe] values. Further, the relative abundance of {sup 26}Mg in the extreme population stars is notably higher than that of {sup 25}Mg, in contrast to model predictions. The {sup 25}Mg/{sup 24}Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.« less

  3. Osmium isotopic homogeneity in the CK carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Goderis, Steven; Brandon, Alan D.; Mayer, Bernhard; Humayun, Munir

    2017-11-01

    Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent

  4. The Abundance and Distribution of Presolar Materials in Cluster IDPS

    NASA Technical Reports Server (NTRS)

    Messenger, Scott; Keller, Lindsay; Nakamura-Messenger, Keiko; Ito, Motoo

    2007-01-01

    Presolar grains and remnants of interstellar organic compounds occur in a wide range of primitive solar system materials, including meteorites, interplanetary dust particles (IDPs), and comet Wild-2 samples. Among the most abundant presolar phases are silicate stardust grains and molecular cloud material. However, these materials have also been susceptible to destruction and alteration during parent body and nebular processing. In addition to their importance as direct samples of remote and ancient astrophysical environments, presolar materials thus provide a measure of how well different primitive bodies have preserved the original solar system starting materials. The matrix normalized abundances of presolar silicate grains in meteorites range from 20 ppm in Semarkona and Bishunpur to 170 ppm for Acfer 094. The lower abundances of presolar silicates in Bishunpur and Semarkona has been ascribed to the destruction of presolar silicates during aqueous processes. Presolar silicates appear to be significantly more abundant in anhydrous IDPs, possibly because these materials did not experience parent body hydrothermal alteration. Among IDPs the estimated abundances of presolar silicates vary by more than an order of magnitude, from 480 to 5500 ppm. The wide disparity in the abundances of presolar silicates of IDPs may be a consequence of the relatively small total area analyzed in those studies and the fine grain sizes of the IDPs. Alternatively, there may be a wide range in presolar silicate abundances between different IDPs. This view is supported by the observation that 15N-rich IDPs have higher presolar silicate abundances than those with isotopically normal N.

  5. The chemical abundance analysis of normal early A- and late B-type stars

    NASA Astrophysics Data System (ADS)

    Fossati, L.; Ryabchikova, T.; Bagnulo, S.; Alecian, E.; Grunhut, J.; Kochukhov, O.; Wade, G.

    2009-09-01

    Context: Modern spectroscopy of early-type stars often aims at studying complex physical phenomena such as stellar pulsation, the peculiarity of the composition of the photosphere, chemical stratification, the presence of a magnetic field, and its interplay with the stellar atmosphere and the circumstellar environment. Comparatively less attention is paid to identifying and studying the “normal” A- and B-type stars and testing how the basic atomic parameters and standard spectral analysis allow one to fit the observations. By contrast, this kind of study is paramount for eventually allowing one to correctly quantify the impact of the various physical processes that occur inside the atmospheres of A- and B-type stars. Aims: We wish to establish whether the chemical composition of the solar photosphere can be regarded as a reference for early A- and late B-type stars. Methods: We have obtained optical high-resolution, high signal-to-noise ratio spectra of three slowly rotating early-type stars (HD 145788, 21 Peg and π Cet) that show no obvious sign of chemical peculiarity, and performed a very accurate LTE abundance analysis of up to 38 ions of 26 elements (for 21 Peg), using a vast amount of spectral lines visible in the spectral region covered by our spectra. Results: We provide an exhaustive description of the abundance characteristics of the three analysed stars with a critical review of the line parameters used to derive the abundances. We compiled a table of atomic data for more than 1100 measured lines that may be used in the future as a reference. The abundances we obtained for He, C, Al, S, V, Cr, Mn, Fe, Ni, Sr, Y, and Zr are compatible with the solar ones derived with recent 3D radiative-hydrodynamical simulations of the solar photosphere. The abundances of the remaining studied elements show some degree of discrepancy compared to the solar photosphere. Those of N, Na, Mg, Si, Ca, Ti, and Nd may well be ascribed to non-LTE effects; for P, Cl, Sc and

  6. Observations of hydrogen and helium isotopes in solar cosmic rays. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Hurford, G. J.

    1974-01-01

    The isotopic composition of hydrogen and helium in solar cosmic rays provides a means of studying solar flare particle acceleration mechanisms since the enhanced relative abundance of rare isotopes, such as H-2, H-3, and He-3, is due to their production by inelastic nuclear collisions in the solar atmosphere during the flare. Electron isotope spectrometer on an IMP spacecraft was used to measure this isotopic composition. The response of the dE/dx-E particle telescope is discussed, and alpha particle channeling in thin detectors is identified as an important background source affecting measurement of low values of (He-3/He-4). The flare-averaged results obtained for the period October, 1972 November, 1973 are given.

  7. Stable isotope analysis of dissolved carbon species of Hot Lake, WA

    NASA Astrophysics Data System (ADS)

    Courtney, S.; Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J.

    2013-12-01

    Hot Lake is a hypersaline, meromictic lake in north-central Washington. The lake is epsomitic, with seasonably-variable salinity (.2 to 2 M magnesium sulfate) and produces carbonates and salt precipitates. The maximum depth of the lake is around 2.5 m, and below a thermocline there is intense solar heat retention in the monolimnion, often exceeding 50°C. Despite these extreme and variable conditions, a microbial mat of up to 1.5 cm thick thrives annually in Hot Lake. The mat is widespread throughout the lake at water depths (during our experiments) ranging from 60cm-140cm. It is comprised of a variety of cyanobacteria along with other autotrophic and heterotrophic bacteria. These populations are visibly stratified with four consistent laminae displaying differences in bacterial pigmentation. Many of the layers contain carbonate species, but the full relationship between the mat and the carbonate crystallization is not known. We are studying the microbial interactions and carbon cycling of the mat communities, using stable isotope analysis of the mat and the lake water, both in situ and ex situ. We are exploring the incorporation and movement of carbon in the mat, spatially and temporally, to understand the fixation mechanisms and metabolic processes at play in this environment. This was done primarily using stable isotope ratio mass spectrometry. The focus of this work is on the study and measurement of dissolved organic and inorganic carbon using a GasBench and IRMS setup, following methods adapted from Lang et al. (2012). To account for the unique chemistry of Hot Lake, trials on the effects of oxidation conditions and salinity were done on lab-synthesized samples to compare to Hot Lake results. The majority of lake water analyses were done in conjunction with a stable isotope probing (SIP) experiment, completed during two 24-hour periods at Hot Lake in June and July of 2013. The SIP experiments included ex situ incubations (in separate glass containers on the

  8. Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

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

    Wall, Andy; Jain, Jinesh; Stewart, Brian

    2012-01-01

    Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

  9. Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

    NASA Technical Reports Server (NTRS)

    Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

    2018-01-01

    The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

  10. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    USGS Publications Warehouse

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  11. 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.

  12. 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

  13. Determination of kinetic isotopic fractionation of water during bare soil evaporation

    NASA Astrophysics Data System (ADS)

    Quade, Maria; Brüggemann, Nicolas; Graf, Alexander; Rothfuss, Youri

    2017-04-01

    A process-based understanding of the water cycle in the atmosphere is important for improving meteorological and hydrological forecasting models. Usually only net fluxes of evapotranspiration - ET are measured, while land-surface models compute their raw components evaporation -E and transpiration -T. Isotopologues can be used as tracers to partition ET, but this requires knowledge of the isotopic kinetic fractionation factor (αK) which impacts the stable isotopic composition of water pools (e.g., soil and plant waters) during phase change and vapor transport by soil evaporation and plant transpiration. It is defined as a function of the ratio of the transport resistances in air of the less to the most abundant isotopologue. Previous studies determined αK for free evaporating water (Merlivat, 1978) or bare soil evaporation (Braud et al. 2009) at only low temporal resolution. The goal of this study is to provide estimates at higher temporal resolution. We performed a soil evaporation laboratory experiment to determine the αK by applying the Craig and Gordon (1965) model. A 0.7 m high column (0.48 m i.d.) was filled with silt loam (20.1 % sand, 14.9 % loam, 65 % silt) and saturated with water of known isotopic composition. Soil volumetric water content, temperature and the isotopic composition (δ) of the soil water vapor were measured at six different depths. At each depth microporous polypropylene tubing allowed the sampling of soil water vapor and the measurement of its δ in a non-destructive manner with high precision and accuracy as detailed in Rothfuss et al. (2013). In addition, atmospheric water vapor was sampled at seven different heights up to one meter above the surface for isotopic analysis. Results showed that soil and atmospheric δ profiles could be monitored at high temporal and vertical resolutions during the course of the experiment. αK could be calculated by using an inverse modeling approach and the Keeling (1958) plot method at high temporal

  14. Evaluation of Kilauea Eruptions By Using Stable Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Rahimi, K. E.; Bursik, M. I.

    2016-12-01

    Kilauea, on the island of Hawaii, is a large volcanic edifice with numerous named vents scattered across its surface. Halema`uma`u crater sits with Kilauea caldera, above the magma reservoir, which is the main source of lava feeding most vents on Kilauea volcano. Halema`uma`u crater produces basaltic explosive activity ranging from weak emission to sub-Plinian. Changes in the eruption style are thought to be due to the interplay between external water and magma (phreatomagmatic/ phreatic), or to segregation of gas from magma (magmatic) at shallow depths. Since there are three different eruption mechanisms (phreatomagmatic, phreatic, and magmatic), each eruption has its own isotope ratios. The aim of this study is to evaluate the eruption mechanism by using stable isotope analysis. Studying isotope ratios of D/H and δ18O within fluid inclusion and volcanic glass will provide an evidence of what driven the eruption. The results would be determined the source of water that drove an eruption by correlating the values with water sources (groundwater, rainwater, and magmatic water) since each water source has a diagnostic value of D/H and δ18O. These results will provide the roles of volatiles in eruptions. The broader application of this research is that these methods could help volcanologists forecasting and predicting the current volcanic activity by mentoring change in volatiles concentration within deposits.

  15. High Resolution Gamma Ray Analysis of Medical Isotopes

    NASA Astrophysics Data System (ADS)

    Chillery, Thomas

    2015-10-01

    Compton-suppressed high-purity Germanium detectors at the University of Massachusetts Lowell have been used to study medical radioisotopes produced at Brookhaven Linac Isotope Producer (BLIP), in particular isotopes such as Pt-191 used for cancer therapy in patients. The ability to precisely analyze the concentrations of such radio-isotopes is essential for both production facilities such as Brookhaven and consumer hospitals across the U.S. Without accurate knowledge of the quantities and strengths of these isotopes, it is possible for doctors to administer incorrect dosages to patients, thus leading to undesired results. Samples have been produced at Brookhaven and shipped to UML, and the advanced electronics and data acquisition capabilities at UML have been used to extract peak areas in the gamma decay spectra. Levels of Pt isotopes in diluted samples have been quantified, and reaction cross-sections deduced from the irradiation parameters. These provide both cross checks with published work, as well as a rigorous quantitative framework with high quality state-of-the-art detection apparatus in use in the experimental nuclear physics community.

  16. The Carbon Isotope Ratio in Local Molecular Clouds

    NASA Astrophysics Data System (ADS)

    Goto, Miwa; Usuda, Tomonori; Takato, Naruhisa; Masahiko, Hayashi; Sakamoto, Seiichi; Mitchell, George

    We report the carbon isotope ratio in nearby molecular clouds LkHα 101, AFGL 490, and Mon R2 IRS 3. The vibrational transition bands of 12CO ν = 2 ← 0 and 13CO ν = 1 ← 0 were observed with high resolution near-infrared spectroscopy (R = 23,000) to measure the relative abundance of 13CO to 12CO. The isotopic ratios are 12CO/13CO = 1379 (LkHα 101), 8649 (AFGL 490), and 158 (Mon R2 IRS 3), which is twice higher than in the solar neighborhood. The molecular clouds are with high visible extinction (AV = 10 70 mag), well shielded from destructive FUV field. It is questionable that the selective photo-destruction of 13CO plays a major role in biasing isotope ratio. Uncertainty in the Doppler parameters of the unresolved absorption lines, and possible emission filling of fundamental transitions are suspected to account for the high 12CO/13CO ratio. Higher resolution spectroscopy (R ~ 100,000) is the key to go for the accurate measurement of isotope ratio.

  17. Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

    NASA Astrophysics Data System (ADS)

    Young, E. D.

    2007-12-01

    Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for

  18. Reprint Of: Enhanced spatially-resolved trace analysis using combined SIMS-single-stage AMS

    NASA Astrophysics Data System (ADS)

    Grabowski, K. S.; Groopman, E. E.; Fahey, A. J.

    2018-01-01

    Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20-50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

  19. Testing sequential extraction methods for the analysis of multiple stable isotope systems from a bone sample

    NASA Astrophysics Data System (ADS)

    Sahlstedt, Elina; Arppe, Laura

    2017-04-01

    Stable isotope composition of bones, analysed either from the mineral phase (hydroxyapatite) or from the organic phase (mainly collagen) carry important climatological and ecological information and are therefore widely used in paleontological and archaeological research. For the analysis of the stable isotope compositions, both of the phases, hydroxyapatite and collagen, have their more or less well established separation and analytical techniques. Recent development in IRMS and wet chemical extraction methods have facilitated the analysis of very small bone fractions (500 μg or less starting material) for PO43-O isotope composition. However, the uniqueness and (pre-) historical value of each archaeological and paleontological finding lead to preciously little material available for stable isotope analyses, encouraging further development of microanalytical methods for the use of stable isotope analyses. Here we present the first results in developing extraction methods for combining collagen C- and N-isotope analyses to PO43-O-isotope analyses from a single bone sample fraction. We tested sequential extraction starting with dilute acid demineralization and collection of both collagen and PO43-fractions, followed by further purification step by H2O2 (PO43-fraction). First results show that bone sample separates as small as 2 mg may be analysed for their δ15N, δ13C and δ18OPO4 values. The method may be incorporated in detailed investigation of sequentially developing skeletal material such as teeth, potentially allowing for the investigation of interannual variability in climatological/environmental signals or investigation of the early life history of an individual.

  20. Correlation between isotopic and meteorological parameters in Italian wines: a local-scale approach.

    PubMed

    Aghemo, Costanza; Albertino, Andrea; Gobetto, Roberto; Spanna, Federico

    2011-08-30

    Since the beginning of the 1980s deuterium nuclear magnetic resonance and carbon-13 mass spectrometry have proved to be reliable techniques for detecting adulteration and for classifying natural products by their geographic origin. Scientific literature has so far mainly focused on data acquired at regional level where isotopic parameters are correlated to climatic mean data relative to large territories. Nebbiolo and Barbera wine samples of various vintages and from different areas within the Piedmont region (northern Italy) were analysed using SNIF-NMR and GC-C-IRMS and a large set of meteorological parameters were recorded by means of weather stations placed in fields where the grapes were grown. Correlations between isotopic ((2)H and (13)C) data and several climatic parameters at a local level (mean temperature, total rainfall, mean humidity and thermal sums) were attempted and some linear correlations were found. Mean temperature and total rainfall were found to be correlated to isotopic ((2)H and (13)C) abundance in linear direct and inverse proportions respectively. Lower or no correlations between deuterium and carbon-13 abundances and other meteorological parameters such as mean humidity and thermal sums were found. Moreover, wines produced from different grape varieties in the same grape field showed significantly different isotopic values. Copyright © 2011 Society of Chemical Industry.

  1. Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

    NASA Technical Reports Server (NTRS)

    Williford, Kenneth H.; Ushikubo, Takayuki; Lepot, Kevin; Hallmann, Christian; Spicuzza, Michael J.; Eigenbrode, Jennifer L.; Summons, Roger E.; Valley, John W.

    2011-01-01

    Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous

  2. Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

    PubMed

    Centler, Florian; Heße, Falk; Thullner, Martin

    2013-09-01

    At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways. © 2013.

  3. Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.

    1989-01-01

    A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

  4. Depletion of highly abundant proteins in blood plasma by ammonium sulfate precipitation for 2D-PAGE analysis.

    PubMed

    Mahn, Andrea; Ismail, Maritza

    2011-11-15

    Ammonium sulfate precipitation (ASP) was explored as a method for depleting some highly abundant proteins from blood plasma, in order to reduce the dynamic range of protein concentration and to improve the detection of low abundance proteins by 2D-PAGE. 40% ammonium sulfate saturation was chosen since it allowed depleting 39% albumin and 82% α-1-antitrypsin. ASP-depletion showed high reproducibility in 2D-PAGE analysis (4.2% variation in relative abundance of albumin), similar to that offered by commercial affinity-depletion columns. Besides, it allowed detecting 59 spots per gel, very close to the number of spots detected in immuno-affinity-depleted plasma. Thus, ASP at 40% saturation is a reliable depletion method that may help in proteomic analysis of blood plasma. Finally, ASP-depletion seems to be complementary to hydrophobic interaction chromatography (HIC)-depletion, and therefore an ASP-step followed by a HIC-step could probably deplete the most highly abundant plasma proteins, thus improving the detection of low abundance proteins by 2D-PAGE. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Equilibrium lithium isotope fractionation in Li-rich minerals

    NASA Astrophysics Data System (ADS)

    Liu, S.; Li, Y.; Liu, J.

    2017-12-01

    Lithium is the lightest alkali metal, and only exhibits +1 valence state in minerals. It is widely distributed on the Earth, and usually substitutes for Mg in silicate minerals. Li has two stable isotopes, 6Li and 7Li, with the relative abundances of 7.52% and 92.48%, respectively. The large mass difference between 6Li and 7Li could induce significant isotope fractionation in minerals. Li isotopes can provide an important geochemical tracer for mantle processes. However, the fractionation factors for Li in most minerals remain poorly known, which makes the geochemical implications of Li isotope fractionations in minerals difficult to assess. Here, we try to use the vibrational frequencies obtained by the first-principles methods based on density-functional theory to calculate the Li isotope fractionation parameters for amblygonite (LiAlPO4F), bikitaite (LiSi2AlO7H2), eucryptite (LiAlSiO4), lithiophilite (LiMnPO4), lithiophosphate (Li3PO4), montebrasite (LiAlPO5H), and spodumene (LiAlSi2O6) in the temperature range of 0-1200 ºC. For forsterite (Mg2SiO4) and diopside (CaMgSi2O6) in which Li takes the place of Mg, the equilibrium Li isotope fractionation between them also be studied. Our preliminary calculations show that the coordination number of Li seems to play an important role in controlling Li isotope fractionation in these minerals, and concentration of Li in forsterite and diopside seems to have great effects on Li isotope fractionation factors of them.

  6. The ruthenium isotopic composition of the oceanic mantle

    NASA Astrophysics Data System (ADS)

    Bermingham, K. R.; Walker, R. J.

    2017-09-01

    The approximately chondritic relative, and comparatively high absolute mantle abundances of the highly siderophile elements (HSE), suggest that their concentrations in the bulk silicate Earth were primarily established during a final ∼0.5 to 1% of ;late accretion; to the mantle, following the cessation of core segregation. Consequently, the isotopic composition of the HSE Ru in the mantle reflects an amalgamation of the isotopic compositions of late accretionary contributions to the silicate portion of the Earth. Among cosmochemical materials, Ru is characterized by considerable mass-independent isotopic variability, making it a powerful genetic tracer of Earth's late accretionary building blocks. To define the Ru isotopic composition of the oceanic mantle, the largest portion of the accessible mantle, we report Ru isotopic data for materials from one Archean and seven Phanerozoic oceanic mantle domains. A sample from a continental lithospheric mantle domain is also examined. All samples have identical Ru isotopic compositions, within analytical uncertainties, indicating that Ru isotopes are well mixed in the oceanic mantle, defining a μ100Ru value of 1.2 ± 7.2 (2SD). The only known meteorites with the same Ru isotopic composition are enstatite chondrites and, when corrected for the effects of cosmic ray exposure, members of the Main Group and sLL subgroup of the IAB iron meteorite complex which have a collective CRE corrected μ100Ru value of 0.9 ± 3.0. This suggests that materials from the region(s) of the solar nebula sampled by these meteorites likely contributed the dominant portion of late accreted materials to Earth's mantle.

  7. Re-Os isotopic systematics of primitive lavas from the Lassen region of the Cascade arc, California

    USGS Publications Warehouse

    Borg, L.E.; Brandon, A.D.; Clynne, M.A.; Walker, R.J.

    2000-01-01

    Rhenium-osmium isotopic systematics of primitive calc-alkaline lavas from the Lassen region appear to be controlled by mantle wedge processes. Lavas with a large proportion of slab component have relatively low Re and Os abundances, and have radiogenic Os and mid ocean ridge basalt-like Sr and Pb isotopic compositions. Lavas with a small proportion of slab component have higher Re and Os elemental abundances and display mantle-like Os, Sr, Nd, and Pb isotopic compositions. Assimilation with fractional crystallization can only generate the Re-Os systematics of the Lassen lavas from a common parent if the distribution coefficient for Re in sulfide is ~40-1100 times higher than most published estimates and if most incompatible element abundances decrease during differentiation. High Re/Os ratios in mid ocean ridge basalts makes subducted oceanic crust a potential source of radiogenic Os in volcanic arcs. The slab beneath the southernmost Cascades is estimated to have 187Os/188Os ratios as high as 1.4. Mixing between a slab component and mantle wedge peridotite can generate the Os isotopic systematics of the Lassen lavas provided the slab component has a Sr/Os ratio of ~7.5X105 and Os abundances that are 100-600 times higher than mid ocean ridge basalts. For this model to be correct, Os must be readily mobilized and concentrated in the slab component, perhaps as a result of high water and HCl fugacities in this subduction environment. Another possible mechanism to account for the correlation between the magnitude of the subduction geochemical signature and Os isotopic composition involves increasing the stability of an Os-bearing phase in mantle wedge peridotites as a result of fluxing with the slab component. Melting of such a source could yield low Os magmas that are more susceptible to crustal contamination, and hence have more radiogenic Os isotopic compositions, than magmas derived from sources with a smaller contribution from the slab. Thus, the addition of the

  8. The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

    NASA Astrophysics Data System (ADS)

    Schrader, Devin L.; Franchi, Ian A.; Connolly, Harold C., Jr.; Greenwood, Richard C.; Lauretta, Dante S.; Gibson, Jenny M.

    2011-01-01

    To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ 17O-intercept of -2.23 ± 0.14 (2σ). Thin sections of Al Rais, Shişr 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the

  9. Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

    PubMed

    Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

    2015-07-01

    To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH <10 gave too low (15)N/(14)N ratios indicating an incomplete derivatization; in contrast, too high (15)N/(14)N ratios at pH >10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

  10. Preparative separation of underivatized amino acids for compound-specific stable isotope analysis and radiocarbon dating of hydrolyzed bone collagen.

    PubMed

    Tripp, Jennifer A; McCullagh, James S O; Hedges, Robert E M

    2006-01-01

    Analysis of stable and radioactive isotopes from bone collagen provides useful information to archaeologists about the origin and age of bone artifacts. Isolation and analysis of single amino acids from the proteins can provide additional and more accurate information by removing contamination and separating a bulk isotope signal into its constituent parts. In this paper, we report a new method for the separation and isolation of underivatized amino acids from bone collagen, and their analysis by isotope ratio MS and accelerator MS. RP chromatography is used to separate the amino acids with nonpolar side chains, followed by an ion pair separation to isolate the remaining amino acids. The method produces single amino acids with little or no contamination from the separation process and allows for the measurement of accurate stable isotope ratios and pure samples for radiocarbon dating.

  11. Experimental and theoretical oscillator strengths of Mg I for accurate abundance analysis

    NASA Astrophysics Data System (ADS)

    Pehlivan Rhodin, A.; Hartman, H.; Nilsson, H.; Jönsson, P.

    2017-02-01

    Context. With the aid of stellar abundance analysis, it is possible to study the galactic formation and evolution. Magnesium is an important element to trace the α-element evolution in our Galaxy. For chemical abundance analysis, such as magnesium abundance, accurate and complete atomic data are essential. Inaccurate atomic data lead to uncertain abundances and prevent discrimination between different evolution models. Aims: We study the spectrum of neutral magnesium from laboratory measurements and theoretical calculations. Our aim is to improve the oscillator strengths (f-values) of Mg I lines and to create a complete set of accurate atomic data, particularly for the near-IR region. Methods: We derived oscillator strengths by combining the experimental branching fractions with radiative lifetimes reported in the literature and computed in this work. A hollow cathode discharge lamp was used to produce free atoms in the plasma and a Fourier transform spectrometer recorded the intensity-calibrated high-resolution spectra. In addition, we performed theoretical calculations using the multiconfiguration Hartree-Fock program ATSP2K. Results: This project provides a set of experimental and theoretical oscillator strengths. We derived 34 experimental oscillator strengths. Except from the Mg I optical triplet lines (3p 3P°0,1,2-4s 3S1), these oscillator strengths are measured for the first time. The theoretical oscillator strengths are in very good agreement with the experimental data and complement the missing transitions of the experimental data up to n = 7 from even and odd parity terms. We present an evaluated set of oscillator strengths, gf, with uncertainties as small as 5%. The new values of the Mg I optical triplet line (3p 3P°0,1,2-4s 3S1) oscillator strength values are 0.08 dex larger than the previous measurements.

  12. Analysis of tarnished plant bug movement using carbon and nitrogen isotopes

    USDA-ARS?s Scientific Manuscript database

    Tarnished plant bug, Lygus lineolaris (Palisot de Beauvois), is the primary pest of cotton across the Midsouth of the United States. Movement into cotton fields occurs during the summer from other host plants, both cultivated and wild. Stable isotope analysis (SIA) has been used in other studies to ...

  13. Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--discrimination of ammonium nitrate sources.

    PubMed

    Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

    2009-06-01

    An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures. The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid. Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed. The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material.

  14. Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

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

    Lee, Brady D.; Moran, James J.; Nims, Megan K.

    Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

  15. A Formation Timescale of the Galactic Halo from Mg Isotopes in Dwarf Stars

    NASA Astrophysics Data System (ADS)

    Carlos, Marília; Karakas, Amanda I.; Cohen, Judith G.; Kobayashi, Chiaki; Meléndez, Jorge

    2018-04-01

    We determine magnesium isotopic abundances of metal-poor dwarf stars from the galactic halo, to shed light on the onset of asymptotic giant branch (AGB) star nucleosynthesis in the galactic halo and constrain the timescale of its formation. We observed a sample of eight new halo K dwarfs in a metallicity range of ‑1.9 < [Fe/H] < ‑0.9 and 4200 < T eff(K) < 4950, using the HIRES spectrograph at the Keck Observatory (R ≈ 105 and 200 ≤ S/N ≤ 300). We obtain magnesium isotopic abundances by spectral synthesis on three MgH features and compare our results with galactic chemical evolution models. With the current sample, we almost double the number of metal-poor stars with Mg isotopes determined from the literature. The new data allow us to determine the metallicity when the 26Mg abundances start to become important, [Fe/H] ∼ ‑1.4 ± 0.1. The data with [Fe/H] > ‑1.4 are somewhat higher (1–3σ) than previous chemical evolution model predictions, indicating perhaps higher yields of the neutron-rich isotopes. Our results using only AGB star enrichment suggest a timescale for formation for the galactic halo of about 0.3 Gyr, but considering also supernova enrichment, the upper limit for the timescale formation is about 1.5 Gyr. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

  16. 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.

  17. Compound-specific stable isotope analysis of nitrogen-containing intact polar lipids.

    PubMed

    Svensson, Elisabeth; Schouten, Stefan; Stam, Axel; Middelburg, Jack J; Sinninghe Damsté, Jaap S

    2015-12-15

    Compound-specific isotope analysis (CSIA) of nitrogen in amino acids has proven a valuable tool in many fields (e.g. ecology). Several intact polar lipids (IPLs) also contain nitrogen, and their nitrogen isotope ratios have the potential to elucidate food-web interactions or metabolic pathways. Here we have developed novel methodology for the determination of δ(15)N values of nitrogen-containing headgroups of IPLs using gas chromatography coupled with isotope-ratio mass spectrometry. Intact polar lipids with nitrogen-containing headgroups were hydrolyzed and the resulting compounds were derivatized by (1) acetylation with pivaloyl chloride for compounds with amine and hydroxyl groups or (2) esterification using acidified 2-propanol followed by acetylation with pivaloyl chloride for compounds with both carboxyl and amine groups. The δ(15)N values of the derivatives were subsequently determined using gas chromatography/combustion/isotope-ratio mass spectrometry. Intact polar lipids with ethanolamine and amino acid headgroups, such as phosphatidylethanolamine and phosphatidylserine, were successfully released from the IPLs and derivatized. Using commercially available pure compounds it was established that δ(15)N values of ethanolamine and glycine were not statistically different from the offline-determined values. Application of the technique to microbial cultures and a microbial mat showed that the method works well for the release and derivatization of the headgroup of phosphatidylethanolamine, a common IPL in bacteria. A method to enable CSIA of nitrogen of selected IPLs has been developed. The method is suitable for measuring natural stable nitrogen isotope ratios in microbial lipids, in particular phosphatidylethanolamine, and will be especially useful for tracing the fate of nitrogen in deliberate tracer experiments. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth

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

    Shepherd, Thomas J.; British Geological Survey, Keyworth, Nottingham; Dirks, Wendy

    We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and {sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5–8 years, living in NE England. By integrating the isotope datamore » with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2–3 years for molars, first 1–2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2 µg Pb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.126–2.079) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.879–0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM{sub 10}, PM{sub 2.5}) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4 µgPb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.145–2.117) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.898–0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1–2 months) were readily identified, together with evidence that dentine provides a good proxy for

  19. Stable isotope deltas: Tiny, yet robust signatures in nature

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

  20. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  1. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

  2. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

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

    Isselhardt, Brett H.

    2011-09-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/ 238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser inmore » a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.« less

  3. PPAK wide-field Integral Field Spectroscopy of NGC 628 - II. Emission line abundance analysis

    NASA Astrophysics Data System (ADS)

    Rosales-Ortega, F. F.; Díaz, A. I.; Kennicutt, R. C.; Sánchez, S. F.

    2011-08-01

    In this second paper of the series, we present the two-dimensional (2D) emission line abundance analysis of NGC 628, the largest object within the PPAK Integral Field Spectroscopy (IFS) Nearby Galaxies Survey, PINGS. We introduce the methodology applied to the 2D IFS data in order to extract and deal with large spectral samples, from which a 2D abundance analysis can be later performed. We obtain the most complete and reliable abundance gradient of the galaxy up to date, by using the largest number of spectroscopic points sampled in the galaxy, and by comparing the statistical significance of different strong-line metallicity indicators. We find features not previously reported for this galaxy that imply a multimodality of the abundance gradient consistent with a nearly flat distribution in the innermost regions of the galaxy, a steep negative gradient along the disc and a shallow gradient or nearly constant metallicity beyond the optical edge of the galaxy. The N/O ratio seems to follow the same radial behaviour. We demonstrate that the observed dispersion in metallicity shows no systematic dependence with the spatial position, signal-to-noise ratio or ionization conditions, implying that the scatter in abundance for a given radius is reflecting a true spatial physical variation of the oxygen content. Furthermore, by exploiting the 2D IFS data, we were able to construct the 2D metallicity structure of the galaxy, detecting regions of metal enhancement and showing that they vary depending on the choice of the metallicity estimator. The analysis of axisymmetric variations in the disc of NGC 628 suggest that the physical conditions and the star formation history of different symmetric regions of the galaxy have evolved in a different manner. Based on observations made at the Centro Astronómico Hispano Alemán (CAHA) at Calar Alto, operated jointly by the Max-Planck Institut für Astronomie and the Instituto de Astrofísica de Andalucía (CSIC).

  4. Alpha-capture reaction rates for 22 Ne (α , n) via sub-Coulomb alpha-transfer and its effect on final abundances of s-process isotopes

    NASA Astrophysics Data System (ADS)

    Jayatissa, Heshani; Rogachev, Grigory; Koshchiy, Yevgeny; Goldberg, Vladilen; Hooker, Joshua; Hunt, Curtis; Magana, Cordero; Roeder, Brian; Saastamoinen, Antti; Spiridon, Alexandria; Upadhyayula, Sriteja; Trippella, Oscar

    2017-09-01

    The 22 Ne (α , n) reaction is a very important neutron source reaction for the slow neutron capture process (s-process) in asymptotic giant branch stars. These direct measurements are very difficult to carry out at the energy regimes of interest for astrophysics (Gamow energies) due to the extremely small reaction cross section. The large uncertainties introduced when extrapolating direct measurements at high energies down to the Gamow energies can be overcome by measuring the Asymptotic Normalization Coefficients (ANC) of the relevant states using α-transfer reactions at sub-Coulomb energies to reduce the optical model dependence. The study of the 22Ne(6Li,d) and 22Ne(7Li,t) reaction was carried out at the Cyclotron Institute at Texas A&M University. The α-ANC measurements for the near α-threshold resonances of 26Mg provide constraints for the 22Ne(α,n) reaction rate. The effect of this reaction rate on the final abundances of the s-process isotopes will be discussed.

  5. Clustering in the stellar abundance space

    NASA Astrophysics Data System (ADS)

    Boesso, R.; Rocha-Pinto, H. J.

    2018-03-01

    We have studied the chemical enrichment history of the interstellar medium through an analysis of the n-dimensional stellar abundance space. This work is a non-parametric analysis of the stellar chemical abundance space. The main goal is to study the stars from their organization within this abundance space. Within this space, we seek to find clusters (in a statistical sense), that is, stars likely to share similar chemo-evolutionary history, using two methods: the hierarchical clustering and the principal component analysis. We analysed some selected abundance surveys available in the literature. For each sample, we labelled the group of stars according to its average abundance curve. In all samples, we identify the existence of a main enrichment pattern of the stars, which we call chemical enrichment flow. This flow is set by the structured and well-defined mean rate at which the abundances of the interstellar medium increase, resulting from the mixture of the material ejected from the stars and stellar mass-loss and interstellar medium gas. One of the main results of our analysis is the identification of subgroups of stars with peculiar chemistry. These stars are situated in regions outside of the enrichment flow in the abundance space. These peculiar stars show a mismatch in the enrichment rate of a few elements, such as Mg, Si, Sc and V, when compared to the mean enrichment rate of the other elements of the same stars. We believe that the existence of these groups of stars with peculiar chemistry may be related to the accretion of planetary material on to stellar surfaces or may be due to production of the same chemical element by different nucleosynthetic sites.

  6. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    PubMed

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  7. Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

    PubMed

    Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

    2017-05-01

    In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

  8. Calcium Isotope Systematics During Development of the Domestic Chicken (Gallus gallus)

    NASA Astrophysics Data System (ADS)

    Wheatley, P. V.

    2003-12-01

    Calcium isotope distributions have been recognized as showing systematic and predictable fractionation in nature. However, most of the observed calcium isotope fractionation to date is due to biological processes. The presence of abundant amounts of calcium in mineralized tissues makes the isotopic system of calcium particularly valuable in biological and paleobiological questions involving biomineralization. In order to apply calcium isotope systematics to paleobiological questions the changes in the calcium isotope signatures of mineralized tissue in modern animals should be studied. My study observed the domestic chicken (Gallus gallus) through embryologic ontogeny. This was accomplished by obtaining fertilized eggs staged in a growth series from day 12 to day 20. The eggs were dissected and shell, embryonic bone, albumen, and yolk were analyzed in order to characterize the calcium isotopic composition of the individual components over the course of the growth series. Several systematic changes in the isotopic signatures of various tissues were observed during the course of the development of the embryos. In general, mineralization in biological systems preferentially partitions the lighter isotopes of calcium into hard parts. As a result of this fractionation during mineralization, partitioning of light isotopes of calcium into the mineralized tissues may result in residual tissues being enriched in the heavier isotopes as ontogeny progresses. Better understanding of the behavior of calcium in modern biological systems will improve its application to fossils and expand the number of paleobiological and evolutionary questions that can be addressed using calcium isotopic data.

  9. Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

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

    Zappala, J. C.; Bailey, K.; Mueller, P.

    In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

  10. Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

    DOE PAGES

    Zappala, J. C.; Bailey, K.; Mueller, P.; ...

    2017-03-11

    In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

  11. Stable Isotope Identification of Nitrogen Sources for United States (U.S.) Pacific Coast Estuaries

    NASA Astrophysics Data System (ADS)

    Brown, C. A.; Kaldy, J. E.; Fong, P.; Fong, C.; Mochon Collura, T.; Clinton, P.

    2016-02-01

    Nutrients are the leading cause of water quality impairments in the United States, and as a result tools are needed to identify the sources of nutrients. We used natural abundance stable isotope data to evaluate nitrogen sources to U.S. west coast estuaries. We collected macroalgae and analyzed these samples for natural abundance of stable isotopes (δ15N) and supplemented this with available data from the literature for estuaries from Mexico to Alaska. Stable isotope ratios of green macroalgae were compared to δ15N of dissolved inorganic nitrogen of oceanic and watershed end members. There was a latitudinal gradient in δ15N of macroalgae with southern estuaries being 7 per mil heavier than northern estuaries. Gradients in isotope data were compared to nitrogen sources estimated by the USGS using the SPARROW model. In California estuaries, the elevation of isotope data appeared to be related to anthropogenic nitrogen sources. In Oregon systems, the nitrogen levels of streams flowing into the estuaries are related to forest cover, rather than to developed land classes. In Oregon estuaries, the δ15N of macroalgae suggested that the ocean and nitrogen-fixing trees in the watersheds were the dominant nitrogen sources with heavier sites located near the estuary mouth. In California estuaries, the gradient was reversed with heavier sites located upriver. In some Oregon estuaries, there was an elevation an elevation of δ15N above marine end members in the vicinity of wastewater treatment facility discharge locations, suggesting isotopes may be useful for distinguishing inputs along an estuarine gradient.

  12. Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

    USGS Publications Warehouse

    Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

    2012-01-01

    The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

  13. The Chelyabinsk Fall Highly Siderophile Element Abundance and 187Os/188Os Composition and Comparison with Ordinary and Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Day, J. M. D.; Corder, C. A.; Dhaliwal, J. K.; Liu, Y.; Taylor, L. A.

    2014-09-01

    New osmium isotope and highly siderophile element abundance data are presented for the Chelyabinsk ordinary chondrite fall (February 2013) and placed into context with new data for ordinary and carbonaceous chondrites.

  14. Project VeSElkA: abundance analysis of chemical species in HD 41076 and HD 148330

    NASA Astrophysics Data System (ADS)

    Khalack, V.; Gallant, G.; Thibeault, C.

    2017-10-01

    A new semi-automatic approach is employed to carry out the abundance analysis of high-resolution spectra of HD 41076 and HD 148330 obtained recently with the spectropolarimetre Echelle SpectroPolarimetric Device for Observations of Stars at the Canada-France-Hawaii Telescope. This approach allows to prepare in a semi-automatic mode the input data for the modified zeeman2 code and to analyse several hundreds of line profiles in sequence during a single run. It also provides more information on abundance distribution for each chemical element at the deeper atmospheric layers. Our analysis of the Balmer profiles observed in the spectra of HD 41076 and HD 148330 has resulted in the estimates of their effective temperature, gravity, metallicity and radial velocity. The respective models of stellar atmosphere have been calculated with the code phoenix and used to carry out abundance analysis employing the modified zeeman2 code. The analysis shows a deficit of the C, N, F, Mg, Ca, Ti, V, Cu, Y, Mo, Sm and Gd, and overabundance of Cr, Mn, Fe, Co, Ni, Sr, Zr, Ba, Ce, Nd and Dy in the stellar atmosphere of HD 41076. In the atmosphere of HD 148330, the C, N and Mo appear to be underabundant, while the Ne, Na, Al, Si, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Sr, Y, Zr, Ba, Ce, Pr, Nd, Sm, Eu, Gd and Dy are overabundant. We also have found signatures of vertical abundance stratification of Fe, Ti, Cr and Mn in HD 41076, and of Fe, Ti, V, Cr, Mn, Y, Zr, Ce, Nd, Sm and Gd in HD 148330.

  15. Comparison of distributed reacceleration and leaky-box models of cosmic-ray abundances (Z = 3-28)

    NASA Technical Reports Server (NTRS)

    Letaw, John R.; Silberberg, Rein; Tsao, C. H.

    1993-01-01

    A large collection of elemental and isotopic cosmic-ray data has been analyzed using the leaky-box transport model with and without reacceleration in the interstellar medium. Abundances of isotopes and elements with charges Z = 3-28 and energies E = 10 MeV/nucleon-1 TeV/nucleon were explored. Our results demonstrate that reacceleration models make detailed and accurate predictions with the same number of parameters or fewer as standard leaky-box models. Ad hoc fitting parameters in the standard model are replaced by astrophysically significant reacceleration parameters. Distributed reacceleration models explain the peak in secondary-to-primary ratios around 1 GeV/nucleon. They diminish the discrepancy between rigidity-dependent leakage and energy-independent anisotropy. They also offer the possibility of understanding isotopic anomalies at low energy.

  16. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  17. 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.

  18. Solar abundance of silicon

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

    Holweger, H.

    1973-07-01

    An analysis of 19 photospheric Si I lines whose oscillator strengths have recently been detertmined by Garz (1973) leads to a solar abundance of silicon, log epsilon /sub Si/ = 7.65 plus or minus 0.07, on the scale where log epsilon /sub H/ = 12. Together with the sodium abundance determained earlier by the same method, a solar abundance ratio /sup epsilon /Na//sup epsilon /Si = 0.045 ( plus or minus 10%) results. Within the error limits this a grees wtth the meteoritic ratio found in carbonaceous chondrites. Results concerning line-broadening by hydrogen are discussed. (auth)

  19. Comparison of IRMS and NMR spectrometry for the determination of intramolecular 13C isotope composition: application to ethanol.

    PubMed

    Gilbert, Alexis; Hattori, Ryota; Silvestre, Virginie; Wasano, Nariaki; Akoka, Serge; Hirano, Satoshi; Yamada, Keita; Yoshida, Naohiro; Remaud, Gérald S

    2012-09-15

    Isotopic (13)C NMR is a relatively recent technique which allows the determination of intramolecular (13)C isotope composition at natural abundance. It has been used in various scientific fields such as authentication, counterfeiting or plant metabolism. Although its precision has already been evaluated, the determination of its trueness remains still challenging. To deal with that issue, a comparison with another normalized technique must be achieved. In this work, we compare the intramolecular (13)C isotope distribution of ethanol from different origins obtained using both Isotope Ratio Mass Spectrometry (IRMS) and Nuclear Magnetic Resonance (NMR) spectrometry techniques. The IRMS approach consists of the oxidation of ethanol to acetic acid followed by the degradation of the latter for the analysis of each fragments formed. We show here that the oxidation of ethanol to acetic acid does not bring any significant error on the determination of the site-specific δ(13)C (δ(13)C(i)) of ethanol using the IRMS approach. The difference between the data obtained for 16 samples from different origins using IRMS and NMR approaches is not statistically significant and remains below 0.3‰. These results are encouraging for the future studies using isotopic NMR, especially in combination with the IRMS approach. Copyright © 2012. Published by Elsevier B.V.

  20. Oxygen abundances in halo stars

    NASA Astrophysics Data System (ADS)

    Bessell, Michael S.; Sutherland, Ralph S.; Ruan, Kui

    1991-12-01

    The present study determines the oxygen abundance for a sample of metal-poor G dwarfs by analysis of OH lines between 3080 and 3200 A and the permitted high-excitation far-red O I triple. The oxygen abundances determined from the low-excitation OH lines are up to 0.55 dex lower than those measured from the high-excitation O I lines. The abundances for the far-red O I triplet lines agree with those rederived from Abia and Rebolo (1989), and the abundances from the OH lines in dwarfs and giants are in agreement with the rederived O abundances of Barbuy (1988) and others from the forbidden resonance O I line. Because the chi = 0.1.7 eV OH lines are formed in the same layers as the majority of Fe, Ti, and other neutral metal lines used for abundance analyses, it is argued that the OH lines and the forbidden O I line yield the true oxygen abundances relative to the metals.