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Sample records for level isotope ratio

  1. SPATIAL VARIABILITY IN MUSSELS USED TO ASSESS BASE LEVEL NITROGEN ISOTOPE RATIO IN FRESHWATER ECOSYSTEMS

    EPA Science Inventory

    Freshwater mussels have been used to establish base level nitrogen isotope ratio values ( 15N) used in trophic position and food web studies in freshwater ecosystems. In this study, we assess the variability introduced when using unionid mussels in this manner by investigating th...

  2. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals.

    PubMed

    Jaouen, Klervia; Szpak, Paul; Richards, Michael P

    2016-01-01

    Carbon and nitrogen stable isotope ratios of bone collagen are an established method for dietary reconstruction, but this method is limited by the protein preservation. Zinc (Zn) is found in bioapatite and the isotopic compositions of this element constitute a very promising dietary indicator. The extent of fractionation of Zn isotopes in marine environments, however, remains unknown. We report here on the measurement of zinc, carbon and nitrogen isotopes in 47 marine mammals from the archaeological site of Arvik in the Canadian Arctic. We undertook this study to test and demonstrate the utility of Zn isotopes in recent mammal bone minerals as a dietary indicator by comparing them to other isotopic dietary tracers. We found a correlation between δ66Zn values and trophic level for most species, with the exception of walruses, which may be caused by their large seasonal movements. δ6Zn values can therefore be used as a dietary indicator in marine ecosystems for both modern and recent mammals. PMID:27010907

  3. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals

    PubMed Central

    Jaouen, Klervia; Szpak, Paul; Richards, Michael P.

    2016-01-01

    Carbon and nitrogen stable isotope ratios of bone collagen are an established method for dietary reconstruction, but this method is limited by the protein preservation. Zinc (Zn) is found in bioapatite and the isotopic compositions of this element constitute a very promising dietary indicator. The extent of fractionation of Zn isotopes in marine environments, however, remains unknown. We report here on the measurement of zinc, carbon and nitrogen isotopes in 47 marine mammals from the archaeological site of Arvik in the Canadian Arctic. We undertook this study to test and demonstrate the utility of Zn isotopes in recent mammal bone minerals as a dietary indicator by comparing them to other isotopic dietary tracers. We found a correlation between δ66Zn values and trophic level for most species, with the exception of walruses, which may be caused by their large seasonal movements. δ6Zn values can therefore be used as a dietary indicator in marine ecosystems for both modern and recent mammals. PMID:27010907

  4. Detecting isotopic ratio outliers

    SciTech Connect

    Bayne, C.K.; Smith, D.H.

    1985-01-01

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers. 6 refs., 3 figs., 3 tabs.

  5. Nitrogen stable isotope ratio in the manila clam, Ruditapes philippinarum, reflects eutrophication levels in tidal flats.

    PubMed

    Watanabe, Satoshi; Kodama, Masashi; Fukuda, Masaaki

    2009-10-01

    Understanding the effects of anthropogenic eutrophication on coastal fisheries may help in the enhancement of fishery production by effective utilization of sewage effluents, as well as in the consequent reduction of eutrophication. In this study, it was revealed that the nitrogen stable isotope ratio (delta(15)N) in the soft tissues of the manila clam, Ruditapes philippinarum, can be used as an indicator of anthropogenic eutrophication levels in tidal flat environments by investigation of delta(15)N in dissolved inorganic nitrogen (DIN), particulate organic matter (POM), sedimentary organic matter (SOM) and soft tissues of the clam in five tidal flats in Japan with different levels of DIN concentration. In addition, it was found that the acid insoluble fraction of the shell organic matrix, conchiolin, can be used as a proxy for the soft tissues in delta(15)N analyses. This will contribute in easier storage handling and the expansion of chances for sample acquisition. PMID:19647270

  6. Isotopic Ratio, Isotonic Ratio, Isobaric Ratio and Shannon Information Uncertainty

    NASA Astrophysics Data System (ADS)

    Ma, Chun-Wang; Wei, Hui-Ling

    2014-11-01

    The isoscaling and the isobaric yield ratio difference (IBD) probes, both of which are constructed by yield ratio of fragment, provide cancelation of parameters. The information entropy theory is introduced to explain the physical meaning of the isoscaling and IBD probes. The similarity between the isoscaling and IBD results is found, i.e., the information uncertainty determined by the IBD method equals to β - α determined by the isoscaling (α (β) is the parameter fitted from the isotopic (isotonic) yield ratio).

  7. Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

    SciTech Connect

    Liezers, Martin; Lehn, Scott A; Olsen, Khris B; Farmer, Orville T; Duckworth, Douglas C

    2009-10-01

    Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by the applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.

  8. Levels of mercury and organochlorine compounds and stable isotope ratios in three tuna species taken from different regions of Japan.

    PubMed

    Hisamichi, Yohsuke; Haraguchi, Koichi; Endo, Tetsuya

    2010-08-01

    Levels of mercury (Hg) and organochlorine compounds (OCs), such as PCBs and p,p'-DDE, as well as the stable isotope ratios of carbon (delta 13C) and nitrogen (delta 15N) were compared in Pacific bluefin, yellowfin, and albacore tuna taken from the southern, central, and northern regions of Japan according to tuna species and the region of origin. Levels of Hg and OCs as well as the delta 15N value were the highest in the bluefin tuna, reflecting their higher trophic position and longer life span. The average Hg concentrations tended to be higher in specimens taken in the southern region than in the central and northern regions for bluefin tuna and in the southern region than in the central region for yellowfin and albacore tuna, while the levels of OCs tended to be lower in the southern region except for yellowfin tuna. The spatial differences in Hg and OCs levels found in the three species may reflect geographical differences in the contamination of marine environment around Japan. Negative correlations between delta 13C and delta 15N were found in the yellowfin and albacore tuna, probably reflecting the latitudinal effect, whereas a positive correlation was found in the bluefin tuna, probably reflecting a diet shift during wide-range migration. PMID:20604561

  9. Isotopic ratios in planetary atmospheres.

    PubMed

    de Bergh, C

    1995-03-01

    Recent progress on measurements of isotopic ratios in planetary or satellite atmospheres include measurements of the D/H ratio in the methane of Uranus, Neptune and Titan and in the water of Mars and Venus. Implications of these measurements on our understanding of the formation and evolution of the planets and satellite are discussed. Our current knowledge of the carbon, nitrogen and oxygen isotopic ratios in the atmospheres of these planets, as well as on Jupiter and Saturn, is also reviewed. We finally show what progress can be expected in the very near future due to some new ground-based instrumentation particularly well suited to such studies, and to forthcoming space missions. PMID:11539257

  10. 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

  11. Laser spectroscopic measurement of helium isotope ratios.

    SciTech Connect

    Wang, L.-B.; Mueller, P.; Holt, R. J.; Lu, Z.-T.; O'Connor, T. P.; Sano, Y.; Sturchio, N.; Univ. of Illinois; Univ. of Tokyo; Univ. of Illinois at Chicago

    2003-06-13

    A sensitive laser spectroscopic method has been applied to the quantitative determination of the isotope ratio of helium at the level of {sup 3}He/{sup 4}He = 10{sup -7}--10{sup -5}. The resonant absorption of 1083 nm laser light by the metastable {sup 3}He atoms in a discharge cell was measured with the frequency modulation saturation spectroscopy technique while the abundance of {sup 4}He was measured by a direct absorption technique. The results on three different samples extracted from the atmosphere and commercial helium gas were in good agreement with values obtained with mass spectrometry. The achieved 3{sigma} detection limit of {sup 3}He in helium is 4 x 10{sup -9}. This demonstration required a 200 {mu}L STP sample of He. The sensitivity can be further improved, and the required sample size reduced, by several orders of magnitude with the addition of cavity enhanced spectroscopy.

  12. 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

  13. 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

  14. The CN isotopic ratios in comets

    NASA Astrophysics Data System (ADS)

    Manfroid, J.; Jehin, E.; Hutsemékers, D.; Cochran, A.; Zucconi, J.-M.; Arpigny, C.; Schulz, R.; Stüwe, J. A.; Ilyin, I.

    2009-08-01

    Our aim is to determine the isotopic ratios 12C/13C and 14N/15N in a variety of comets and link these measurements to the formation and evolution of the solar system. The 12C/13C and 14N/15N isotopic ratios are measured for the CN radical by means of high-resolution optical spectra of the R branch of the B-X (0, 0) violet band. 23 comets from different dynamical classes have been observed, sometimes at various heliocentric and nucleocentric distances, in order to estimate possible variations of the isotopic ratios in parent molecules. The 12C/13C and 14N/15N isotopic ratios in CN are remarkably constant (average values of, respectively, 91.0 ± 3.6 and 147.8 ± 5.7) within our measurement errors, for all comets whatever their origin or heliocentric distance. While the carbon isotopic ratio does agree with the terrestrial value (89), the nitrogen ratio is a factor of two lower than the terrestrial value (272), indicating a fractionation in the early solar system, or in the protosolar nebula, common to all the comets of our sample. This points towards a common origin of the comets independently of their birthplaces, and a relationship between HCN and CN. Appendices and Table [see full textsee full textsee full text] are only available in electronic form at http://www.aanda.org Based on observations made with ESO Telescopes at the La Silla Paranal Observatory under programmes ID 268.C-5570, 270.C-5043, 073.C-0525, 274.C-5015 and 075.C-0355(A).

  15. Stable isotope ratios and mercury levels in red meat products from baleen whales sold in Japanese markets.

    PubMed

    Endo, Tetsuya; Hotta, Yohei; Hisamichi, Yohsuke; Kimura, Osamu; Sato, Rie; Haraguchi, Koichi; Funahashi, Naoko; Baker, C Scott

    2012-05-01

    We analyzed the δ(13)C, δ(15)N and δ(18)O values and Hg concentration in red meat products originating from the predominant types sold in Japan for human consumption: two populations of common minke (J- and O-types), Bryde's and sei whales in the western North Pacific Ocean, and fin and Antarctic minke whales in the Southern Ocean. The order of the trophic positions, evaluated by δ(15)N values and Hg concentrations, coincided with their known feeding habits: common minke (J-type)=common minke (O-type)> Bryde's ≥ sei ≥ Antarctic minke ≥ fin. The Hg concentrations in the combined samples from the six samples were significantly correlated with their δ(15)N values (γ=0.455, n=66, p<0.05), reflecting overall differences in the trophic level. This correlation was not significant for within-species comparison for the common minke (J- and O-types) or the Bryde's whale, probably reflecting the higher δ(15)N value and lower Hg concentration in the North Pacific Ocean around Japan. Determination of δ(13)C, δ(15)N and δ(18)O could be used to discriminate between the red meat products originating from the whale species in the North Pacific and Southern Oceans. However, the four whale species or populations in the Pacific Ocean could not be discriminated on basis of these values, nor could the two species in the Southern Ocean. Positive correlations between the δ(13)C and δ(15)N values and negative correlations between the δ(15)N and δ(18)O values and the δ(13)C and δ(18)O values, probably reflecting migration patterns, were found in some whale species in the North Pacific and Southern Oceans. PMID:22364843

  16. Feasibility of Isotopic Measurements: Graphite Isotopic Ratio Method

    SciTech Connect

    Wood, Thomas W.; Gerlach, David C.; Reid, Bruce D.; Morgan, W. C.

    2001-04-30

    This report addresses the feasibility of the laboratory measurements of isotopic ratios for selected trace constituents in irradiated nuclear-grade graphite, based on the results of a proof-of-principal experiment completed at Pacific Northwest National Laboratory (PNNL) in 1994. The estimation of graphite fluence through measurement of isotopic ratio changes in the impurity elements in the nuclear-grade graphite is referred to as the Graphite Isotope Ratio Method (GIRM). Combined with reactor core and fuel information, GIRM measurements can be employed to estimate cumulative materials production in graphite moderated reactors. This report documents the laboratory procedures and results from the initial measurements of irradiated graphite samples. The irradiated graphite samples were obtained from the C Reactor (one of several production reactors at Hanford) and from the French G-2 Reactor located at Marcoule. Analysis of the irradiated graphite samples indicated that replicable measurements of isotope ratios could be obtained from the fluence sensitive elements of Ti, Ca, Sr, and Ba. While these impurity elements are present in the nuclear-grade graphite in very low concentrations, measurement precision was typically on the order of a few tenths of a percent to just over 1 percent. Replicability of the measurements was also very good with measured values differing by less than 0.5 percent. The overall results of this initial proof-of-principal experiment are sufficiently encouraging that a demonstration of GIRM on a reactor scale basis is planned for FY-95.

  17. Isotope Ratios of Cellulose from Plants Having Different Photosynthetic Pathways

    PubMed Central

    Sternberg, Leonel O.; Deniro, Michael J.; Johnson, Hyrum B.

    1984-01-01

    Hydrogen and carbon isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from C3, C4, and Crassulacean acid metabolism (CAM) plants were determined for plants growing within a small area in Val Verde County, Texas. Plants having CAM had distinctly higher deuterium/hydrogen (D/H) ratios than plants having C3 and C4 metabolism. When hydrogen isotope ratios are plotted against carbon isotope ratios, each photosynthetic mode separates into a distinct cluster of points. C4 plants had many D/H ratios similar to those of C3 plants, so that hydrogen isotope ratios cannot be used to distinguish between these two photosynthetic modes. Portulaca mundula, which may have a modified photosynthetic mode between C4 and CAM, had a hydrogen isotope ratio between those of the C4 and CAM plants. When oxygen isotope ratios are plotted against carbon isotope ratios, no distinct clustering of the C4 and CAM plants occurs. Thus, oxygen isotope ratios are not useful in distinguishing between these metabolic modes. A plot of hydrogen isotope ratios versus oxygen isotope ratios for this sample set shows considerable overlap between oxygen isotope ratios of the different photosynthetic modes without a concomitant overlap in the hydrogen isotope ratios of CAM and the other two photosynthetic modes. This observation is consistent with the hypothesis that higher D/H ratios in CAM plants relative to C3 and C4 plants are due to isotopic fractionations occurring during biochemical reactions. PMID:16663460

  18. Isotopic ratio measurements with ICP-MS

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1986-06-03

    An inductively-coupled-plasma source mass spectrometer (ICP-MS) has been used to measure the isotopic composition of U, Pb, Os, and B standards. Particular emphasis has been placed on uranium because of its nuclear and environmental interest and because of the availability of a well-characterized set of standards with a wide range of isotopic compositions. The precision and accuracy obtainable in isotope ratio measurements by ICP-MS depend on many factors including background, interferences, dead time, mass fractionation (bias), abundance sensitivity, and counting statistics. Which, if any, of these factors controls accuracy and precision depends on the type of sample being analyzed and the characteristics of the mass spectrometer. These issues are discussed in detail.

  19. Measuring Isotope Ratios Across the Solar System

    NASA Technical Reports Server (NTRS)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biology [1]. For the Allan Hills 84001 meteorite, for example, the (sup 1)(sup 3)C/(sup 1)(sup 2)C ratio identifies it as a Mars (SNC) meteorite; the ??K/??Ar ratio tells us the last time the rock cooled to solid, namely 4 Gya; isotope ratios in (sup 3)He, (sup 2)(sup 1)Ne and (sup 3)?Ar show it was in space (cosmic ray exposure) for 10-20 million years; (sup 1)?C dating that it sat in Antarctica for 13,000 years before discovery; and clumped isotope analysis of (sup 1)?O(sup 1)(sup 3)C(sup 1)?O in its carbonate that it was formed at 18+/-4 ?C in a near-surface aqueous environment [2]. Solar System Formation

  20. Uranium isotope ratio measurements in field settings

    SciTech Connect

    Shaw, R.W.; Barshick, C.M.; Young, J.P.; Ramsey, J.M.

    1997-06-01

    The authors have developed a technique for uranium isotope ratio measurements of powder samples in field settings. Such a method will be invaluable for environmental studies, radioactive waste operations, and decommissioning and decontamination operations. Immediate field data can help guide an ongoing sampling campaign. The measurement encompasses glow discharge sputtering from pressed sample hollow cathodes, high resolution laser spectroscopy using conveniently tunable diode lasers, and optogalvanic detection. At 10% {sup 235}U enrichment and above, the measurement precision for {sup 235}U/({sup 235}U+{sup 238}U) isotope ratios was {+-}3%; it declined to {+-}15% for 0.3% (i.e., depleted) samples. A prototype instrument was constructed and is described.

  1. Calcium isotope ratios in animal and human bone

    NASA Astrophysics Data System (ADS)

    Reynard, L. M.; Henderson, G. M.; Hedges, R. E. M.

    2010-07-01

    Calcium isotopes in tissues are thought to be influenced by an individual's diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ 44/42Ca) of modern and archaeological animal and human bone ( n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ 44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ 44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ 44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ 44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ 44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.

  2. Oxygen Isotope Ratios in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Brittain, Sean; Najita, Joan; Carr, John; Doppmann, Greg

    2009-08-01

    Meteorites provide important clues about the environment from which our solar system formed. Their mineralogical and isotopic composition provides important insight into the thermal, chemical and dynamical history of the protoplanetary disk. One of the most intriguing discoveries to come from the study of meteorites is the depletion of the ^18O/^16O and ^17O/^16O ratios in the oldest components of meteorites relative to Earth. These measurements suggest that the gas from which the sun condensed was more ^16O-rich than the material from which planets formed. The leading explanation for this isotopic anomaly is the selective dissociation of CO in the outer protoplanetary disk or envelope. The basic premise is that the freed ^17,18O atoms in the outer disk formed water that then enriched the ^17,18O abundance in rocky material. Thus, bodies that formed later (such as planets) were increasingly enriched in ^17,18O. To test this scenario, we will probe the efficiency of selective dissociation of CO in nearby protoplanetary disk systems. We will measure the isotopic ratio of C^17O/C^18O/C^16O by acquiring high-resolution absorption spectra of ro-vibrational CO lines from edge-on disks and envelopes.

  3. Final Report on Isotope Ratio Techniques for Light Water Reactors

    SciTech Connect

    Gerlach, David C.; Gesh, Christopher J.; Hurley, David E.; Mitchell, Mark R.; Meriwether, George H.; Reid, Bruce D.

    2009-07-01

    The Isotope Ratio Method (IRM) is a technique for estimating the energy or plutonium production in a fission reactor by measuring isotope ratios in non-fuel reactor components. The isotope ratios in these components can then be directly related to the cumulative energy production with standard reactor modeling methods.

  4. 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.

  5. Temperature measurements from oxygen isotope ratios of fish otoliths.

    PubMed

    Devereux, I

    1967-03-31

    Measurements have shown that the temperature of a fish's habitat can be deduced from the Oxygen isotope ratio of its otoliths (ear bones). Isotope ratios Obtained from fossil otoliths indicate a water temperature which agrees wiht that found by isotope measurements on associated benthonic foraminifera. PMID:6020293

  6. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  7. ICP-MS for isotope ratio measurement

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The use of stable isotopes in mineral nutrition research has become a fundamental aspect of conducting this research. A gradual transition has occurred, now virtually complete, from radioactive isotope studies to those using stable isotopes. Although primarily used in human research, mineral stable ...

  8. 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).

  9. Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

    2013-04-01

    Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity

  10. GUM Analysis for TIMS and SIMS Isotopic Ratios in Graphite

    SciTech Connect

    Heasler, Patrick G.; Gerlach, David C.; Cliff, John B.; Petersen, Steven L.

    2007-04-01

    This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

  11. Cesium Isotope Ratios as Indicators of Nuclear Power Plant Operations

    SciTech Connect

    Darin Snyder; James Delmore; Troy Tranter; Nick Mann; Michael Abbott; John Olson

    2011-11-01

    There are multiple paths by which radioactive cesium can reach the effluent from reactor operations. The radioactive 135Cs/137Cs ratios are controlled by these paths. In an effort to better understand the origin of this radiation, these 135Cs/137Cs ratios in effluents from three power reactor sites have been measured in offsite samples. These ratios are different from global fallout by up to six fold and as such cannot have a significant component from this source. A cesium ratio for a sample collected outside of the plant boundary provides integration over the operating life of the reactor. A sample collected inside the plant at any given time can be much different from this lifetime ratio. The measured cesium ratios vary significantly for the three reactors and indicate that the multiple paths have widely varying levels of contributions. There are too many ways these isotopes can fractionate to be useful for quantitative evaluations of operating parameters in an offsite sample, although it may be possible to obtain limited qualitative information for an onsite sample.

  12. Cesium isotope ratios as indicators of nuclear power plant operations.

    PubMed

    Delmore, James E; Snyder, Darin C; Tranter, Troy; Mann, Nick R

    2011-11-01

    There are multiple paths by which radioactive cesium can reach the effluent from reactor operations. The radioactive (135)Cs/(137)Cs ratios are controlled by these paths. In an effort to better understand the origin of this radiation, these (135)Cs/(137)Cs ratios in effluents from three power reactor sites have been measured in offsite samples. These ratios are different from global fallout by up to six fold and as such cannot have a significant component from this source. A cesium ratio for a sample collected outside of the plant boundary provides integration over the operating life of the reactor. A sample collected inside the plant at any given time can be much different from this lifetime ratio. The measured cesium ratios vary significantly for the three reactors and indicate that the multiple paths have widely varying levels of contributions. There are too many ways these isotopes can fractionate to be useful for quantitative evaluations of operating parameters in an offsite sample, although it may be possible to obtain limited qualitative information for an onsite sample. PMID:21816522

  13. Using Oxygen Isotopes in Fish Scale Apatite to Reconstruct Past Temperatures and Water Isotope Ratios

    NASA Astrophysics Data System (ADS)

    Lambert, T. D.; Paytan, A.

    2009-12-01

    Oxygen isotope ratios (δ18O) of apatite phosphate in fish bones and teeth vary according to the temperature and δ18O of water during formation. Since isotope ratios in apatite are often well preserved over geologic timescales, fish bones and teeth have been used to determine past environmental conditions. Fish scales offer several advantages over bones and teeth: they are relatively common in certain sedimentary basins, and they are more easily identified to species level. Analysis of paired bone and scale samples will be presented. The data indicate that fish scale apatite similarly records environmental conditions during growth. Thus δ18O of apatite phosphate in fish scales may provide useful paleoecological information and also indicate past environmental conditions.

  14. THE ATOMIC WEIGHTS COMMISSION AND ISOTOPIC ABUNDANCE RATIO DETERMINATIONS.

    SciTech Connect

    HOLDEN, N.E.

    2005-08-07

    Following Thomson's discovery of stable isotopes in non-radioactive chemical elements, the derivation of atomic weight values from mass spectrometric measurements of isotopic abundance ratios moved very slowly. Forty years later, only 3 1/2 % of the recommended values were based on mass spectrometric measurements and only 38% in the first half century. It might be noted that two chemical elements (tellurium and mercury) are still based on chemical measurements, where the atomic weight value calculated from the relative isotopic abundance measurement either agrees with the value from the chemical measurement or the atomic weight value calculated from the relative isotopic abundance measurement falls within the uncertainty of the chemical measurement of the atomic weight. Of the 19 chemical elements, whose atomic weight is based on non-corrected relative isotopic abundance measurements, five of these are two isotope systems (indium, iridium, lanthanum, lutetium and tantalum) and one is a three-isotope system (oxygen).

  15. Utilizing Isotopic Uranium Ratios in Groundwater Evaluations at NFSS

    SciTech Connect

    Rhodes, M.C.; Keil, K.G.; Frederick, W.T.; Papura, T.R.; Leithner, J.S.; Peterson, J.M.; MacDonell, M.M.

    2006-07-01

    The U.S. Army Corps of Engineers (USACE) Buffalo District is currently evaluating environmental contamination at the Niagara Falls Storage Site (NFSS) under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) as part of its Formerly Utilized Sites Remedial Action Program (FUSRAP). The NFSS is located in the Town of Lewiston in western New York and has been used to store uranium-contaminated materials since 1944. Most of the radioactive materials are currently contained in an on-site structure, but past contamination remains in soil and groundwater. As a naturally occurring radionuclide, uranium is present in all groundwater. Because contamination levels at the site are quite low, it can be difficult to distinguish zones that have been impacted by the past releases from those at the high end of the natural background range. The differences in the isotopic ratio of uranium-234 (U-234) to uranium-238 (U-238) between natural groundwater systems and affected areas are being used in an innovative way to better define the nature and extent of groundwater contamination at NFSS. In natural groundwater, the ratio of U-234 to U-238 exceeds 1 due to the alpha particle recoil effect, in which U-234 is preferentially mobilized to groundwater from adjacent rock or soil. This process is very slow, and it can be hundreds to thousands of years before a measurable impact is seen in the isotopic ratio. Thus, as a result of the recoil effect, the ratio of U-234 to U-238 will be higher in natural groundwater than in contaminated groundwater. This means that if site releases were the source of the uranium being measured in groundwater at NFSS, the ratio of U-234 to U-238 would be expected to be very close to 1 (the same ratio that exists in wastes and soil at the site), because not enough time has elapsed for the alpha particle recoil effect to have significantly altered that ratio. From an evaluation of site and regional groundwater data, an isotopic ratio

  16. Isotope yield ratios of fragments from heavy-ion reactions

    SciTech Connect

    Deak, F.; Kiss, A. ); Seres, Z. ); Galonsky, A.; Heilbronn, L. )

    1991-05-01

    Isotope yield ratios produced in collisions of 35 MeV/nucleon {sup 14}N with targets of C, Ni, Ag, and Ho have an exponential dependence on total neutron-to-proton ratio. A statistical multifragmentation model including particle emission from excited fragments predicted such behavior for yield ratios measured earlier at the higher energy of 84 MeV/nucleon.

  17. Symbiodinium Clade Affects Coral Skeletal Isotopic Ratio

    NASA Astrophysics Data System (ADS)

    Carilli, J.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2011-12-01

    The influence of different physiologies of Symbiodinium dinoflagellate symbiont clades on the skeletal chemistry of associated coral hosts has not previously been investigated. This is an important issue because coral skeletons are routinely used for tropical paleoclimatic reconstructions. We analyzed coral skeletal samples collected simultaneously from neighboring colonies off Belize and found that those harboring different clades of Symbiodinium displayed significantly different skeletal oxygen isotopic compositions. We also found evidence for mean shifts in skeletal oxygen isotopic composition after coral bleaching (the loss and potential exchange of symbionts) in two of four longer coral cores from the Mesoamerican Reef, though all experienced similar climatic conditions. Thus, we suggest that symbiont clade identity leaves a signature in the coral skeletal archive and that this influence must be considered for quantitative environmental reconstruction. In addition, we suggest that the skeletal isotopic signature may be used to identify changes in the dominant symbiont clade that have occurred in the past, to identify how common and widespread this phenomenon is--a potential adaptation to climate change.

  18. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    PubMed

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  19. Temperature Dependence of Isotope Ratios in Tree Rings

    PubMed Central

    Libby, L. M.; Pandolfi, L. J.

    1974-01-01

    The stable isotope ratios of carbon, oxygen, and hydrogen have been measured for a German oak in wood samples of roughly three years each, for the years 1712-1954 A.D., and correlated with the existing weather records from England, Basel, and Geneva to evaluate the empirical temperature coefficients. Isotope ratios in a second official oak, measured for the years 1530-1800 A.D., show the cold temperatures of the Little Ice Age interspersed with warm intervals. PMID:16592163

  20. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-01

    The oxygen isotope compositions (delta(18)O) of eclogitic xenoliths from the Roberts Victor kimberlite range from 2 to 8 per mil relative to SMOW (standard mean ocean water). This surprising variation appears to be due to fractional crystallization: the eclogites rich in oxygen-18 represent early crystal accumulates; the eclogites poor in oxygen-18 represent residual liquids. Crystal-melt partitioning probably exceeded 3 per mil and is interpreted to be pressure-dependent. Anomalous enrichment of oxygen-18 in cumulate eclogites relative to ultramafic xenoliths suggests that crystal-melt partitioning increased after melt-formation but prior to crystallization. PMID:17798552

  1. Direct path integral estimators for isotope fractionation ratios

    SciTech Connect

    Cheng, Bingqing; Ceriotti, Michele

    2014-12-28

    Fractionation of isotopes among distinct molecules or phases is a quantum effect which is often exploited to obtain insights on reaction mechanisms, biochemical, geochemical, and atmospheric phenomena. Accurate evaluation of isotope ratios in atomistic simulations is challenging, because one needs to perform a thermodynamic integration with respect to the isotope mass, along with time-consuming path integral calculations. By re-formulating the problem as a particle exchange in the ring polymer partition function, we derive new estimators giving direct access to the differential partitioning of isotopes, which can simplify the calculations by avoiding thermodynamic integration. We demonstrate the efficiency of these estimators by applying them to investigate the isotope fractionation ratios in the gas-phase Zundel cation, and in a few simple hydrocarbons.

  2. Plutonium isotope ratio variations in North America

    SciTech Connect

    Steiner, Robert E; La Mont, Stephen P; Eisele, William F; Fresquez, Philip R; Mc Naughton, Michael; Whicker, Jeffrey J

    2010-12-14

    Historically, approximately 12,000 TBq of plutonium was distributed throughout the global biosphere by thermo nuclear weapons testing. The resultant global plutonium fallout is a complex mixture whose {sup 240}Pu/{sup 239}Pu atom ratio is a function of the design and yield of the devices tested. The average {sup 240}Pu/{sup 239}Pu atom ratio in global fallout is 0.176 + 014. However, the {sup 240}Pu/{sup 239}Pu atom ratio at any location may differ significantly from 0.176. Plutonium has also been released by discharges and accidents associated with the commercial and weapons related nuclear industries. At many locations contributions from this plutonium significantly alters the {sup 240}Pu/{sup 239}Pu atom ratios from those observed in global fallout. We have measured the {sup 240}Pu/{sup 239}Pu atom ratios in environmental samples collected from many locations in North America. This presentation will summarize the analytical results from these measurements. Special emphasis will be placed on interpretation of the significance of the {sup 240}Pu/{sup 239}Pu atom ratios measured in environmental samples collected in the Arctic and in the western portions of the United States.

  3. Dynamical and Microphysical Controls on Subtropical Water Vapor Isotope Ratios: Using New Spectroscopic Measurements to Link Isotopic and Climatic Variability

    NASA Astrophysics Data System (ADS)

    Raudzens Bailey, A.; Nusbaumer, J. M.; Sato, P.; Noone, D. C.

    2014-12-01

    Water vapor isotope ratios are critical in shaping the isotopic composition of paleo-proxies used to interpret past climate. Indeed, previous research suggests speleothems are sensitive to water vapor transport, and experiments currently underway are evaluating the role of Greenlandic vapor in setting the isotopic record of the ice sheet. The recent and rapid spread of commercial vapor isotopic analyzers—based on cavity-enhanced near-infrared laser absorption spectroscopy—is creating unparalleled opportunities to elucidate which climatic factors control the vapor isotopic composition globally. This presentation describes both an exciting application of this new technology and relevant limitations imposed by measurement uncertainties associated with long-term field deployments. Using three years of continuous water vapor isotope ratio observations from Hawaii's Mauna Loa Observatory—one of the longest records of its kind—we evaluate the influence of large-scale dynamics and cloud microphysical processes in establishing the isotopic composition of water vapor during strong convective activity. Despite the fact that vapor isotope ratios tend to decrease with latitude, greater enrichment in Mauna Loa vapor is associated with a westward retraction of the jet stream, which funnels Asiatic outflow southward, while greater depletion is associated with southwesterly low-level flow. Differences in precipitation efficiency—which are verified by differences in aerosol concentration and total scattering—cause this apparent discrepancy. These results suggest local cloud and precipitation processes are more influential than airmass origin in setting the isotope ratios observed during these strong convective events. The length of the Mauna Loa record, meanwhile, presents a unique opportunity to evaluate long-term stability of biases associated with laser-based isotopic analyzers and to discuss calibration strategies best suited for monitoring programs designed to

  4. 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.

  5. Evaluating chlorine isotope effects from isotope ratios and mass spectra of polychlorinated molecules.

    PubMed

    Elsner, Martin; Hunkeler, Daniel

    2008-06-15

    Compound-specific chlorine isotope analysis receives much interest to assess the fate of chlorinated hydrocarbons in contaminated environments. This paper provides a theoretical basis to calculate isotope ratios and quantify isotope fractionation from ion-current ratios of molecular- and fragment-ion multiplets. Because both (35)Cl and (37)Cl are of high abundance, polychlorinated hydrocarbons consist of molecules containing different numbers of (37)Cl denoted as isotopologues. We show that, during reactions, the changes in isotopologue ratios are proportional to changes in the isotope ratio assuming a nonselective isotope distribution in the initial compound. This proportionality extents even to fragments formed in the ion source of a mass spectrometer such as C 2Cl 2 (double dechlorinated fragment of perchloroethylene, PCE). Fractionation factors and kinetic isotope effects (KIE) may, therefore, be evaluated from isotope, isotopologue or even fragment ratios according to conventional simple equations. The proportionality is exact with symmetric molecules such as dichloroethylene (DCE) and PCE, whereas it is approximately true with molecules containing nonreactive positions such as trichloroethylene (TCE). If in the latter case isotope ratios are derived from dechlorinated fragments, e.g., C 2HCl 2, it is important that fragmentation in the ion source affect all molecular positions alike, as otherwise isotopic changes in reactive positions may be underrepresented. PMID:18484745

  6. LITERATURE SURVEY ON ISOTOPIC ABUNDANCE RATIO MEASUREMENTS - 2001-2005

    SciTech Connect

    HOLDEN, N.E.

    2005-08-13

    Along with my usual weekly review of the published literature for new nuclear data, I also search for new candidates for best measurements of isotopic abundances from a single source. Most of the published articles, that I previously had found in the Research Library at the Brookhaven Lab, have already been sent to the members of the Atomic Weights Commission, by either Michael Berglund or Thomas Walczyk. In the last few days, I checked the published literature for any other articles in the areas of natural variations in isotopic abundance ratios, measurements of isotopic abundance ratios on samples of extra-terrestrial material and isotopic abundance ratio measurements performed using ICPMS instruments. Hopefully this information will be of interest to members of the Commission, the sub-committee on isotopic abundance measurements (SIAM), members of the former sub-committee on natural isotopic fractionation (SNIF), the sub-committee on extra-terrestrial isotope ratios (SETIR), the RTCE Task Group and the Guidelines Task Group, who are dealing with ICPMS and TIMS comparisons. In the following report, I categorize the publications in one of four areas. Measurements performed using either positive or negative ions with Thermal Ionization Mass Spectrometer, TIMS, instruments; measurements performed on Inductively Coupled Plasma Mass Spectrometer, ICPMS, instruments; measurements of natural variations of the isotopic abundance ratios; and finally measurements on extra-terrestrial samples with instrumentation of either type. There is overlap in these areas. I selected out variations and ET results first and then categorized the rest of the papers by TIMS and ICPMS.

  7. Understanding radioxenon isotopical ratios originating from radiopharmaceutical facilities

    NASA Astrophysics Data System (ADS)

    Saey, P. R. J.; Ringbom, A.; Bowyer, T. W.; Becker, A.; de Geer, L.-E.; Nikkinen, M.; Payne, R. F.

    2009-04-01

    It was recently shown that radiopharmaceutical facilities (RPF) are major contributors to the general background of 133Xe and other xenon isotopes both in the northern and southern hemisphere. To distinguish a nuclear explosion signal from releases from civil nuclear facilities, not only the activity concentrations but also the ratios of the four different CTBT relevant radioxenon isotopes (131mXe, 133mXe, 133Xe and 135Xe) have to be well understood. First measurements taken recently in and around two of the world's largest RPF's: NTP at Pelindaba, South Africa and IRE at Fleurus, Belgium have been presented. At both sites, also stack samples were taken in close cooperation with the facility operators. The radioxenon in Belgium could be classified in four classes: the normal European background (133Xe activity between 0 - 5 mBq/m3) on one hand and then the samples where all four isotopes were detected with 133mXe/131mXe > 1. In northern South Africa the Pelindaba RPF is in practice the sole source of radioxenon. It generated a background of 133Xe at the measurement site some 230 km to the west of the RPF of 0 - 5 mBq/m3. In the cases where the air from the Pelindaba facility reached the measurement site directly and in a short time period, the 133Xe was higher, also 135Xe was present and in some samples 133mXe as well. The ratios of the activity concentrations of 135Xe/133Xe vs. 133mXe/131mXe (Multiple Isotope Ratio Plot - MIRC) have been analysed. For both facilities, the possible theoretical ratio's for different scenarios were calculated with the information available and compared with the measurements. It was found that there is an excess of 131mXe present in the European samples compared to theoretical calculations. A similar excess has also been seen in samples measured in northern America. In South Africa, neither the environmental samples nor the stack ones contained 131mXe at measurable levels. This can probably be explained by different processes and

  8. Stable isotope ratios of tap water in the contiguous United States

    NASA Astrophysics Data System (ADS)

    Bowen, Gabriel J.; Ehleringer, James R.; Chesson, Lesley A.; Stange, Erik; Cerling, Thure E.

    2007-03-01

    Understanding links between water consumers and climatological (precipitation) sources is essential for developing strategies to ensure the long-term sustainability of water supplies. In pursing this understanding a need exists for tools to study and monitor complex human-hydrological systems that involve high levels of spatial connectivity and supply problems that are regional, rather than local, in nature. Here we report the first national-level survey of stable isotope ratios in tap water, including spatially and temporally explicit samples from a large number of cities and towns across the contiguous United States. We show that intra-annual ranges of tap water isotope ratios are relatively small (e.g., <10‰ for δ2H) at most sites. In contrast, spatial variation in tap water isotope ratios is very large, spanning ranges of 163‰ for δ2H and 23.6‰ for δ18O. The spatial distribution of tap water isotope ratios at the national level is similar to that of stable isotope ratios of precipitation. At the regional level, however, pervasive differences between tap water and precipitation isotope ratios can be attributed to hydrological factors in the water source to consumer chain. These patterns highlight the potential for monitoring of tap water isotope ratios to contribute to the study of regional water supply stability and provide warning signals for impending water resource changes. We present the first published maps of predicted tap water isotope ratios for the contiguous United States, which will be useful in guiding future research on human-hydrological systems and as a tool for applied forensics and traceability studies.

  9. Ca Isotopic Ratios in Igneous Rocks: Some Preliminary Results

    NASA Astrophysics Data System (ADS)

    Huang, S.; Farkas, J.; Jacobsen, S. B.

    2009-12-01

    Calcium (Ca) is the 5th most abundant element on the Earth, and it is an important geochemical and cosmochemical tracer. It has six isotopes and only H and He have a larger percentage mass difference (Δm/m) between the heaviest and the lightest isotopes. Systematic Ca isotopic studies have mostly focused on low-temperature geochemical processes, and most Ca isotopic analyses have been applied on modern and ancient marine carbonates and sulphates, documenting large and systematic isotopic variations, which were used to infer the chemical evolution of seawater. Detailed work on igneous rocks is very limited. Here we show two examples of how stable Ca isotopic ratios can be a useful geochemical tool in understanding igneous processes. Ca isotopic fractionation between coexisting clinopyroxene and orthopyroxene from mantle peridotites: We report Ca isotopic ratios on co-existing clino- and ortho-pyroxenes from Kilbourne Hole and San Carlos mantle peridotites. The 44Ca/40Ca in orthopyroxenes is ~0.5 per mil heavier than that in co-existing clinopyroxenes. Combined with published Ca isotopic data on low-temperature Ca-bearing minerals (calcite, aragonite and barite), we show that the fractionation of Ca isotopes between Ca-bearing minerals (at both low-temperature and high-temperature) is primarily controlled by the strength of Ca-O bond in the minerals. The mineral with shorter (i.e., stronger) Ca-O bond yields heavier Ca isotopic ratio. Using our measured 44Ca/40Ca in mantle pyroxenes and the relative proportions of major Ca-bearing minerals in the upper mantle, the estimated 44Ca/40Ca of the upper mantle is 1.1 per mil heavier relative to the NIST 915a, ~0.1 to 0.2 per mil higher than basalts. Ca isotopic variation in Hawaiian shield lavas: Large geochemical and isotopic variations have been observed in lavas forming the large tholeiitic shields of Hawaiian volcanoes, with lavas from the surface of the Koolau volcano (Makapuu-stage) defining one compositional and

  10. Detection of adulterated honey produced by honeybee (Apis mellifera L.) colonies fed with different levels of commercial industrial sugar (C₃ and C₄ plants) syrups by the carbon isotope ratio analysis.

    PubMed

    Guler, Ahmet; Kocaokutgen, Hasan; Garipoglu, Ali V; Onder, Hasan; Ekinci, Deniz; Biyik, Selim

    2014-07-15

    In the present study, one hundred pure and adulterated honey samples obtained from feeding honeybee colonies with different levels (5, 20 and 100 L/colony) of various commercial sugar syrups including High Fructose Corn Syrup 85 (HFCS-85), High Fructose Corn Syrup 55 (HFCS-55), Bee Feeding Syrup (BFS), Glucose Monohydrate Sugar (GMS) and Sucrose Sugar (SS) were evaluated in terms of the δ(13)C value of honey and its protein, difference between the δ(13)C value of protein and honey (Δδ(13)C), and C4% sugar ratio. Sugar type, sugar level and the sugar type*sugar level interaction were found to be significant (P<0.001) regarding the evaluated characteristics. Adulterations could not be detected in the 5L/colony syrup level of all sugar types when the δ(13)C value of honey, Δδ(13)C (protein-honey), and C4% sugar ratio were used as criteria according to the AOAC standards. However, it was possible to detect the adulteration by using the same criteria in the honeys taken from the 20 and 100 L/colony of HFCS-85 and the 100L/colony of HFCS-55. Adulteration at low syrup level (20 L/colony) was more easily detected when the fructose content of HFCS syrup increased. As a result, the official methods (AOAC, 978.17, 1995; AOAC, 991.41, 1995; AOAC 998.12, 2005) and Internal Standard Carbon Isotope Ratio Analysis could not efficiently detect the indirect adulteration of honey obtained by feeding the bee colonies with the syrups produced from C3 plants such as sugar beet (Beta vulgaris) and wheat (Triticium vulgare). For this reason, it is strongly needed to develop novel methods and standards that can detect the presence and the level of indirect adulterations. PMID:24594168

  11. Stable Isotope Ratios and the Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-06-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbe forensics, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of 247 separate cultures of B. subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variation between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures.

  12. Isotope ratio mass spectrometry - history and terminology in brief.

    PubMed

    Flenker, Ulrich

    2012-12-01

    The history of isotope ratio mass spectrometry (IRMS) is briefly described. It is shown that the fundamental design of isotope ratio mass spectrometers has not changed since the 1940s. The basic findings concerning the natural variation of isotope abundances even date back to the 1930s. Recent improvements in the methodology mainly concern online coupling and analytical peripherals. The nature of isotopic scales necessitates a specific terminology which is unfamiliar to many analysts. However, corresponding guidelines exist that should be adopted by the anti-doping community. Currently, steroids represent the only group of compounds routinely analyzed by IRMS in doping-control. Suggestions are made in respect to a harmonized terminology concerning the nature and origins of steroids. PMID:22972693

  13. Stable Isotope Ratios as Biomarkers of Diet for Health Research

    PubMed Central

    O’Brien, Diane M.

    2016-01-01

    Diet is a leading modifiable risk factor for chronic disease, but it remains difficult to measure accurately due to the error and bias inherent in self-reported methods of diet assessment. Consequently there is a pressing need for more objective biomarkers of diet for use in health research. The stable isotope ratios of light elements are a promising set of candidate biomarkers because they vary naturally and reproducibly among foods, and those variations are captured in molecules and tissues with high fidelity. Recent studies have identified valid isotopic measures of short and long-term sugar intake, meat intake, and fish intake in specific populations. These studies provide a strong foundation for validating stable isotopic biomarkers in the general United States population. Approaches to improve specificity for specific foods are needed, for example, by modeling intake using multiple stable isotope ratios, or by isolating and measuring specific molecules linked to foods of interest. PMID:26048703

  14. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  15. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    NASA Astrophysics Data System (ADS)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  16. High Resolution Double-Focusing Isotope Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Radke, J.; Deerberg, M.; Hilkert, A.; Schlüter, H.-J.; Schwieters, J.

    2012-04-01

    In recent years isotope ratio mass spectrometry has extended to the capability of quantifying very small isotope signatures related with low abundances and simultaneously detecting molecular masses such as isotopomers and isotopologues containing clumped isotopes. Some of those applications are limited by molecular interferences like different gas molecules with the same nominal mass, e.g. Ar/O2, adducts of the same molecule or of different molecules, and very small isotope abundances. The Thermo Scientific MAT 253 ULTRA is the next generation of high precision gas isotope ratio mass spectrometry, which combines a 10 KV gas ionization source (Thermo Scientific MAT 253) with a double focusing multi-collector mass analyzer (Thermo Scientific Neptune) and reduces those limitations by measuring isotope ratios on a larger dynamic range with high precision. Small ion beam requirements and high sensitivity are achieved by signal-to-noise improvements through enhanced ion beam amplification in faraday cups and ion counters. Interfering backgrounds, e.g. interfering isotopologues or isobaric ions of contaminants, are dramatically decreased by a dynamic range increase combined with high evacuation leading to undisturbed ion transmission through the double-focusing analyser. Furthermore, automated gain calibration for mathematical baseline corrections, switchable detector arrays, ion source control, analyser focusing and full data export is controlled under Isodat data control. New reference/sample strategies are under investigation besides incorporation of the continuous-flow technique and its versatile inlet devices. We are presenting first results and applications of the MAT 253 Ultra.

  17. Radioactive halos and ion microprobe measurement of Pb isotope ratios

    NASA Technical Reports Server (NTRS)

    Gentry, R. V.

    1974-01-01

    This investigation was to obtain, if possible, the Pb isotope ratios of both lunar and meteoritic troilite grains by utilizing ion microprobe techniques. Such direct in situ measurement of Pb isotope ratios would eliminate contamination problems inherent in wet chemistry separation procedures, and conceivably determine whether lunar troilite grains were of meteoritic origin. For comparison purposes two samples of meteoritic troilite were selected (one from Canyon Diablo) for analysis along with two very small lunar troilite grains (approximately 50-100 microns). It was concluded that the ion microprobe as presently operating, does not permit the in situ measurement of Pb isotope ratios in lunar or meteoritic troilite. On the basis of these experiments no conclusions could be drawn as to the origin of the lunar troilite grains.

  18. Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Hayes, J. M.

    1994-01-01

    Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

  19. Oxygen isotopic ratios toward molecular clouds in the Galactic disk

    NASA Astrophysics Data System (ADS)

    Li, Hai-Kun; Zhang, Jiang-Shui; Liu, Zhi-Wei; Lu, Deng-Rong; Wang, Min; Wang, Jin

    2016-03-01

    We present our observations of the J = 1 - 0 rotation transitions in molecular isotopes C18O and C17O toward a sample of molecular clouds with different galactocentric distances, using the Delingha 13.7m (DLH 13.7 m) telescope, administered by Purple Mountain Observatory, and its 9-beam SIS receiver. Complementary observations toward several sources with large galactocentric distance are obtained with the IRAM 30m and Mopra 22m telescopes. C18O/C17O abundance ratios reflecting the 18O/17O isotope ratios are obtained from integrated intensity ratios of C18O and C17O. We derived the ratio value for 13 sources covering a galactocentric distance range of 3kpc to 16kpc. In combination with our mapping results that provide a ratio value of 3.01±0.14 in the Galactic center region, it shows that the abundance ratio tends to increase with galactocentric distance, i.e., it supports a radial gradient along the Galactic disk for the abundance ratio. This is consistent with the inside-out formation scenario of our Galaxy. However, our results may suffer from small samples with large galactocentric distance. Combining our data with multi-transition lines of C18O and C17O will be helpful for constraining opacities and abundances and further confirming the Galactic radial gradient shown by the isotope ratio 18O/17O.

  20. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    NASA Astrophysics Data System (ADS)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-06-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols (SOA) has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all primarily formed from the photo-oxidation of aromatic volatile organic compounds (VOC), in the gas phase and particulate matter (PM) together and PM alone was conducted. Since all of the target compounds are secondary products, their concentrations in the atmosphere are in the low ng m-3 range and consequently a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33‰, which is well within the range predicted by mass balance calculations. However, the observed carbon isotope ratios cover a range of nearly 9‰, and approximately 20% of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban centre with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in

  1. Carbon isotope ratio analysis of steroids by high-temperature liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Zhang, Lijun; Thevis, Mario; Piper, Thomas; Jochmann, Maik A; Wolbert, J Benjamin; Kujawinski, Dorothea M; Wiese, Steffen; Teutenberg, Thorsten; Schmidt, Torsten C

    2014-03-01

    Generally, compound-specific isotope analysis of steroids is carried out by gas chromatography combined with isotope ratio mass spectrometry. Thus, a derivatization of the steroids prior to the measurement is compulsory, and a correction of the isotopic data is often necessary. To overcome this limitation, we present a new approach of high-temperature liquid chromatography coupled with photodiode array detection and isotope ratio mass spectrometry (HT-LC/PDA/IRMS) for the carbon isotope ratio analysis of unconjugated steroids. A steroid mixture containing 19-norandrosterone, testosterone, epitestosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol was fully separated on a C4 column under high-temperature elution with water as the sole eluent. The accuracy for isotope analysis (±0.5 ‰) was around 20 μg g(-1) for testosterone, epitestosterone (79 ng steroid absolute on column), and 30 μg g(-1) for 19-norandrosterone, androsterone, and 5β-pregnane-3α,17α,20α-triol (119 ng steroid absolute on column). The applicability of the method was tested by measuring a pharmaceutical gel containing testosterone. With this work, the scope of LC/IRMS applications has been extended to nonpolar compounds. PMID:24491121

  2. Analytical techniques in biomedical stable isotope applications: (isotope ratio) mass spectrometry or infrared spectrometry?

    PubMed

    Stellaard, Frans; Elzinga, Henk

    2005-12-01

    An overview is presented of biomedical applications of stable isotopes in general, but mainly focused on the activities of the Center for Liver, Digestive and Metabolic Diseases of the University Medical Center Groningen. The aims of metabolic studies in the areas of glucose, fat, cholesterol and protein metabolism are briefly explained, as well as the principle of breath testing and the techniques to study body composition and energy expenditure. Much attention is paid to the analytical considerations based upon metabolite concentrations, sample size restrictions, the availability of stable isotope labelled substrates and dose requirements in relation to compound-specific isotope analysis. The instrumental advantages and limitations of the generally used techniques gas chromatography/reaction/isotope ratio mass spectrometry and gas chromatography/mass spectrometry are described as well as the novelties of the recently commercialised liquid chromatography/combustion/isotope ratio mass spectrometry. The present use and future perspective of infrared (IR) spectrometry for clinical and biomedical stable isotope applications are reviewed. In this respect, the analytical demands on IR spectrometry are discussed to enable replacement of isotope ratio mass spectrometry by IR spectrometry, in particular, for the purpose of compound-specific isotope ratio analysis in biological matrices. PMID:16543190

  3. Heavy element stable isotope ratios: analytical approaches and applications.

    PubMed

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies. PMID:23397089

  4. The use of carbon stable isotope ratios in drugs characterization

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Cristea, G.; Bot, A.; Mirel, V.

    2013-11-01

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ13C between batches from -29.7 to -31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between -31.3 to -34.9% for the same type of analgesic, but from different manufactures.

  5. The use of carbon stable isotope ratios in drugs characterization

    SciTech Connect

    Magdas, D. A. Cristea, G. Bot, A. Mirel, V.

    2013-11-13

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ{sup 13}C between batches from −29.7 to −31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between −31.3 to −34.9% for the same type of analgesic, but from different manufactures.

  6. Nucleosynthesis in AGB Stars Traced by Oxygen Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    De Nutte, R.; Decin, L.; Olofsson, H.; de Koter, A.; Lombaert, R.; Milam, S.; Ramstedt, S.

    2015-08-01

    Isotopic ratios are by far the best diagnostic tracers of the stellar origin of elements, as they are very sensitive to the precise conditions in the nuclear burning regions. They allow us to give direct constraints on stellar evolution models and on the progenitor mass. However, up to now different isotopic ratios have been well constrained for only a handful of Asymptotic Giant Branch (AGB) stars. We present new data on isotopologue lines of a well-selected sample of AGB stars, covering the three spectral classes of C-, S- and M-type stars. We report on the first efforts made in determining accurate isotopologue fractions, focusing on oxygen isotopes which are a crucial tracer of the poorly constrained extra mixing processes in stellar atmospheres.

  7. Isotope Ratios Reveal Trickery in the Produce Aisle

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 2007

    2007-01-01

    A new technique for the proper checking and banning of organic food items is proposed. The analysis of the nitrogen isotope ratio present in the food is found to be a perfect standard for the organic checking of the food products.

  8. Uranium Isotope Ratios in Modern and Precambrian Soils

    NASA Astrophysics Data System (ADS)

    DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

    2015-12-01

    Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

  9. Seawater calcium isotope ratios across the Eocene-Oligocene transition

    USGS Publications Warehouse

    Griffith, E.M.; Paytan, A.; Eisenhauer, A.; Bullen, T.D.; Thomas, E.

    2011-01-01

    During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (??44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater ??44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater ??44/40Ca shifts. This suggests that the response of seawater ??44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms. ?? 2011 Geological Society of America.

  10. Areal Distribution of the Oxygen-Isotope Ratio in Greenland

    NASA Technical Reports Server (NTRS)

    Zwally, H. Jay; Giovinetto, Mario B.

    1997-01-01

    Mean values of the oxygen-isotope ratio relative to standard mean ocean water reported for 46 sites on the Greenland ice sheet are compiled together with data on mean annual surface temperature, latitude, 6180 elevation, and mean annual shortest distance to the open ocean denoted by the 10% sea-ice concentration boundary. Stepwise regression analyses, with 6180 as the dependent variable, define two robust models. In the forward mode at the 99.9% confidence level, only temperature enters the model. In the backward mode at the 95% confidence level, only temperature, latitude, and distance to the open ocean remain in the model. Inversions of the models on the basis of 160 gridpoint locations 100 km apart in the area delimited by the surface equilibrium line produce four contoured distributions of 6"0. Two distributions are based on the bivariate model and two on the multivariate model. The second distribution for each model is obtained substituting mean annual surface-temperature values obtained from the Nimbus-7 Temperature Humidity Infrared Radiometer (THIR) database. All four distributions are considered valid, and differences between them are evaluated using contoured anomaly maps. It is suggested that the inversion of the multivariate model using THIR data provides the more reliable pattern for studies of atmospheric advection or for the derivation of ice-flow adjustments for 6180 series obtained from deep-core or ablation-zone sites.

  11. A Time-Measurement System Based on Isotopic Ratios.

    SciTech Connect

    Vo, Duc T.; Karpius, P. J.; MacArthur, D. W.; Thron, J. L.

    2007-01-01

    A time-measurement system can be built based on the ratio of gamma-ray peak intensities from two radioactive isotopes. The ideal system would use a parent isotope with a short half-life decaying to a long half-life daughter. The activities of the parent-daughter isotopes would be measured using a gamma-ray detector system. The time can then be determined from the ratio of the activities. The best-known candidate for such a system is the {sup 241}Pu-{sup 241}Am parent-daughter pair. However, this {sup 241}Pu-{sup 241}Am system would require a high-purity germanium detector system and sophisticated software to separate and distinguish between the many gamma-ray peaks produced by the decays of the two isotopes. An alternate system would use two different isotopes, again one with a short half-life and one with a half-life that is long relative to the other. The pair of isotopes {sup 210}Pb and {sup 241}Am (with half-lives of 22 and 432 years, respectively) appears suitable for such a system. This time-measurement system operates by measuring the change in the ratio of the 47-keV peak of {sup 210}Pb to the 60-keV peak of {sup 241}Am. For the system to work reasonably well, the resolution of the detector would need to be such that the two gamma-ray peaks are well separated so that their peak areas can be accurately determined using a simple region-of-interest (ROI) method. A variety of detectors were tested to find a suitable system for this application. The results of these tests are presented here.

  12. Predicting the Hydrogen Isotope Ratios of Leaf Waxes Across Landscapes

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Berke, M. A.; Hambach, B.; Ehleringer, J. R.

    2014-12-01

    Leaf wax n-alkanes 2H/1H ratios are widely used as a proxy of paleoprecipitation in climate reconstruction. While the broad nature of the relationships between n-alkane δ2H values and climate are appreciated on geologic scales, the quantitative details of what this proxy is reflecting remain ambiguous on plant and ecosystem levels. Areas of uncertainty on these smaller scales of importance to geologic interpretations are both the biosynthetic fractionation and the leaf-growth interval that is recorded by the isotope signal. To clarify these details, we designed a series of experiments in which modern plants were grown under controlled and monitored conditions. To determine the biosynthetic fractionation, we analyzed n-alkanes from plant grown hydroponically on isotopically distinct waters and under contrasting and controlled humidities. We observed δ2H values of n-alkane were linearly related to growth water δ2H values, but with slope differences associated with humidity. These findings suggested leaf water were central controls on δ2H values of n-alkane and support a relatively constant biosynthetic fractionation factor between leaf water and n-alkanes. To determine the interval that the leaf wax isotope signal reflects, we studied a species naturally growing on water with a constant δ2H value. Here we found the δ2H values of n-alkanes recorded only a two-week period during leaf flush and did not vary thereafter. These data indicated the δ2H values of n-alkanes record conditions early in the season, rather than integrating over the entire growing season. Using these data, we are beginning to develop geospatial predictions of the δ2H values of n-alkane across landscapes for given climate conditions, plant phenologies, and ecosystems. These emerging modeling tools may be used to assess modern ecosystem dynamics, to estimate weathering of leaf waxes to geologic repositories, and to define and test paleoclimate reconstructions from the δ2H values of n-alkanes.

  13. NUSIMEP-7: uranium isotope amount ratios in uranium particles.

    PubMed

    Truyens, J; Stefaniak, E A; Aregbe, Y

    2013-11-01

    The Institute for Reference Materials and Measurements (IRMM) has extensive experience in the development of isotopic reference materials and the organization of interlaboratory comparisons (ILC) for nuclear measurements in compliance with the respective international guidelines (ISO Guide 34:2009 and ISO/IEC 17043:2010). The IRMM Nuclear Signatures Interlaboratory Measurement Evaluation Program (NUSIMEP) is an external quality control program with the objective of providing materials for measurements of trace amounts of nuclear materials in environmental matrices. Measurements of the isotopic ratios of the elements uranium and plutonium in small amounts, typical of those found in environmental samples, are required for nuclear safeguards and security, for the control of environmental contamination and for the detection of nuclear proliferation. The measurement results of participants in NUSIMEP are evaluated according to international guidelines in comparison to independent external certified reference values with demonstrated metrological traceability and uncertainty. NUSIMEP-7 focused on measurements of uranium isotope amount ratios in uranium particles aiming to support European Safeguards Directorate General for Energy (DG ENER), the International Atomic Energy Agency's (IAEA) network of analytical laboratories for environmental sampling (NWAL) and laboratories in the field of particle analysis. Each participant was provided two certified test samples: one with single and one with double isotopic enrichment. These NUSIMEP test samples were prepared by controlled hydrolysis of certified uranium hexafluoride in a specially designed aerosol deposition chamber at IRMM. Laboratories participating in NUSIMEP-7 received the test samples of uranium particles on two graphite disks with undisclosed isotopic ratio values n((234)U)/n((238)U), n((235)U)/n((238)U) and n((236)U)/n((238)U). The uranium isotope ratios had to be measured using their routine analytical

  14. Finite mixture models for the computation of isotope ratios in mixed isotopic samples

    NASA Astrophysics Data System (ADS)

    Koffler, Daniel; Laaha, Gregor; Leisch, Friedrich; Kappel, Stefanie; Prohaska, Thomas

    2013-04-01

    Finite mixture models have been used for more than 100 years, but have seen a real boost in popularity over the last two decades due to the tremendous increase in available computing power. The areas of application of mixture models range from biology and medicine to physics, economics and marketing. These models can be applied to data where observations originate from various groups and where group affiliations are not known, as is the case for multiple isotope ratios present in mixed isotopic samples. Recently, the potential of finite mixture models for the computation of 235U/238U isotope ratios from transient signals measured in individual (sub-)µm-sized particles by laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was demonstrated by Kappel et al. [1]. The particles, which were deposited on the same substrate, were certified with respect to their isotopic compositions. Here, we focus on the statistical model and its application to isotope data in ecogeochemistry. Commonly applied evaluation approaches for mixed isotopic samples are time-consuming and are dependent on the judgement of the analyst. Thus, isotopic compositions may be overlooked due to the presence of more dominant constituents. Evaluation using finite mixture models can be accomplished unsupervised and automatically. The models try to fit several linear models (regression lines) to subgroups of data taking the respective slope as estimation for the isotope ratio. The finite mixture models are parameterised by: • The number of different ratios. • Number of points belonging to each ratio-group. • The ratios (i.e. slopes) of each group. Fitting of the parameters is done by maximising the log-likelihood function using an iterative expectation-maximisation (EM) algorithm. In each iteration step, groups of size smaller than a control parameter are dropped; thereby the number of different ratios is determined. The analyst only influences some control

  15. MAGNESIUM ISOTOPE RATIOS IN {omega} CENTAURI RED GIANTS

    SciTech Connect

    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}Mg 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.

  16. ISOTOPIC RATIOS IN TITAN's METHANE: MEASUREMENTS AND MODELING

    SciTech Connect

    Nixon, C. A.; Achterberg, R. K.; Temelso, B.; Vinatier, S.; Bezard, B.; Coustenis, A.; Teanby, N. A.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G. J.; Jennings, D. E.; Romani, P. N.; Flasar, F. M.

    2012-04-20

    The existence of methane in Titan's atmosphere ({approx}6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of {approx}20 Myr. In this paper, we examine the clues available from isotopic ratios ({sup 12}C/{sup 13}C and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH{sub 4} collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: {sup 13}CH{sub 4}, {sup 12}CH{sub 3}D, and {sup 13}CH{sub 3}D. From these we compute estimates of {sup 12}C/{sup 13}C = 86.5 {+-} 8.2 and D/H = (1.59 {+-} 0.33) Multiplication-Sign 10{sup -4}, in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH{sub 4} + C{sub 2}H {yields} CH{sub 3} + C{sub 2}H{sub 2}. Using these new measurements and predictions we proceed to model the time evolution of {sup 12}C/{sup 13}C and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH{sub 4}), we find that the present-day {sup 12}C/{sup 13}C implies that the CH{sub 4} entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing. We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric

  17. Isotopic Ratios in Titan's Methane: Measurements and Modeling

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Temelso, B.; Vinatier, S.; Teanby, N. A.; Bezard, B.; Achterberg, R. K.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G.; Jennings, D. E.; Romani, P. N.; Coustenis, A.; Flasar, F. M.

    2012-01-01

    The existence of methane in Titan's atmosphere (approx. 6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of approx 20 Myr. In this paper, we examine the clues available from isotopic ratios (C-12/C-13 and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH4 collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: (13)CH4, (12)CH3D, and (13)CH3D. From these we compute estimates of C-12/C-13 = 86.5 +/- 8.2 and D/H = (1.59 +/- 0.33) x 10(exp -4) , in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH4 + C2H yields CH3 + C2H2. Using these new measurements and predictions we proceed to model the time evolution of C-12/C-13 and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH4), we find that the present-day C-12/C-13 implies that the CH4 entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing, We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric methane.

  18. Lignin methoxyl hydrogen isotope ratios in a coastal ecosystem

    NASA Astrophysics Data System (ADS)

    Feakins, Sarah J.; Ellsworth, Patricia V.; Sternberg, Leonel da Silveira Lobo

    2013-11-01

    Stable hydrogen isotope ratios of plant lignin methoxyl groups have recently been shown to record the hydrogen isotopic composition of meteoric water. Here we extend this technique towards tracing water source variations across a saltwater to freshwater gradient in a coastal, subtropical forest ecosystem. We measure the hydrogen isotopic composition of xylem water (δDxw) and methoxyl hydrogen (δDmethoxyl) to calculate fractionations for coastal mangrove, buttonwood and hammock tree species in Sugarloaf Key, as well as buttonwoods from Miami, both in Florida, USA. Prior studies of the isotopic composition of cellulose and plant leaf waxes in coastal ecosystems have yielded only a weak correlation to source waters, attributed to leaf water effects. Here we find δDmethoxyl values range from -230‰ to -130‰, across a 40‰ range in δDxw with a regression equation of δDmethoxyl ‰ = 1.8 * δDxw - 178‰ (R2 = 0.48, p < 0.0001, n = 74). This is comparable within error to the earlier published relationship for terrestrial trees which was defined across a much larger 125‰ isotopic range in precipitation. Analytical precision for measurements of δD values of pure CH3I by gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is σ = 6‰ (n = 31), which is considerably better than for CH3I liberated through cleavage with HI from lignin with σ = 18‰ (n = 26). Our results establish that δDmethoxyl can record water sources and salinity incursion in coastal ecosystems, where variations sufficiently exceed method uncertainties (i.e., applications with δD excursions >50‰). For the first time, we also report yields of propyl iodide, which may indicate lignin synthesis of propoxyl groups under salt-stress.

  19. Utilizing Isotopic Uranium Ratios in Groundwater Evaluations at FUSRAP Sites

    SciTech Connect

    Frederick, W.T.; Keil, K.G.; Rhodes, M.C.; Peterson, J.M.; MacDonell, M.M.

    2007-07-01

    The U.S. Army Corps of Engineers Buffalo District is evaluating environmental radioactive contamination at several Formerly Utilized Sites Remedial Action Program (FUSRAP) sites throughout New York, Pennsylvania, Ohio, and Indiana. The investigations follow the process defined in the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Groundwater data from the Niagara Falls Storage Site (NFSS) in Lewiston, New York were evaluated for isotopic uranium ratios, specifically uranium-234 versus uranium-238 (U- 234 and U-238, respectively), and the results were presented at Waste Management 2006. Since uranium naturally occurs in all groundwater, it can be difficult to distinguish where low-concentration impacts from past releases differ from the high end of a site-specific natural background range. In natural groundwater, the ratio of U-234 to U-238 exceeds 1 (unity) due to the alpha particle recoil effect, in which U-234 is preferentially mobilized to groundwater from adjacent rock or soil. This process is very slow and may take hundreds to thousands of years before a measurable increase is seen in the natural isotopic ratio. If site releases are the source of uranium being measured in groundwater, the U-234 to U-238 ratio is commonly closer to 1, which normally reflects FUSRAP-related, uranium-contaminated wastes and soils. This lower ratio occurs because not enough residence time has elapsed since the 1940's and 1950's for the alpha particle recoil effect to have significantly altered the contamination-derived ratio. An evaluation of NFSS-specific and regional groundwater data indicate that an isotopic ratio of 1.2 has been identified as a signature value to help distinguish natural groundwater, which may have a broad background range, from zones impacted by past releases. (authors)

  20. D/H isotope ratios in the global hydrologic cycle

    NASA Astrophysics Data System (ADS)

    Good, Stephen P.; Noone, David; Kurita, Naoyuki; Benetti, Marion; Bowen, Gabriel J.

    2015-06-01

    Deuterium to hydrogen (D/H) ratios in Earth's hydrologic cycle have long served as important tracers of climate processes, yet the global HDO budget remains poorly constrained because of uncertainties in the isotopic compositions of continental evapotranspiration and runoff. Here bias-corrected satellite retrievals of HDO and H2O concentrations from the Tropospheric Emissions Spectrometer are used to estimate the marine atmospheric surface layer HDO vapor pressure deficit, from which we calculate the global flux-weighted average oceanic evaporation isotopic composition as -37.6‰. Using these estimates, combined with D/H ratios in precipitation, global mass balance suggests H isotope compositions for global runoff and terrestrial evapotranspiration of -77.3‰ and -40.0‰, respectively. By resolving the HDO budget, we establish an accurate global baseline for geochemically enabled Earth system models, demonstrate patterns in entrainment of moisture into the marine surface layer, and determine the isotopic composition of continental fluxes critical for global ecohydrologic investigations.

  1. Accurate and Precise Zinc Isotope Ratio Measurements in Urban Aerosols

    NASA Astrophysics Data System (ADS)

    Weiss, D.; Gioia, S. M. C. L.; Coles, B.; Arnold, T.; Babinski, M.

    2009-04-01

    We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of δ66Zn determinations in aerosols is around 0.05 per mil per atomic mass unit. The method was tested on aerosols collected in Sao Paulo City, Brazil. The measurements reveal significant variations in δ66Zn ranging between -0.96 and -0.37 per mil in coarse and between -1.04 and 0.02 per mil in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source.

  2. Position-specific measurement of oxygen isotope ratios in cellulose: Isotopic exchange during heterotrophic cellulose synthesis

    NASA Astrophysics Data System (ADS)

    Waterhouse, John S.; Cheng, Shuying; Juchelka, Dieter; Loader, Neil J.; McCarroll, Danny; Switsur, V. Roy; Gautam, Lata

    2013-07-01

    We describe the first reported method for the measurement of oxygen isotope ratios at each position in the glucose units of the cellulose molecule. The overall process comprises a series of synthetic organic sequences, by which α-cellulose is hydrolysed to glucose, and oxygen atoms at specific positions in the glucose molecule are removed in samples of benzoic acid for measurement of δ18O. Values of δ18O at specific positions in cellulose are calculated from these δ18O values and the overall δ18O value of the cellulose. We apply the method to determine the degree to which oxygen atoms at each position undergo isotopic exchange with water during heterotrophic cellulose synthesis, such as occurs in the cambium of trees. To do this we extract α-cellulose from wheat seedlings germinated in the dark in aqueous media of differing oxygen isotope ratios. Results indicate that oxygen atoms at positions 5 and 6 (O-5 and O-6 respectively) undergo around 80% exchange with medium water, O-3 undergoes around 50% exchange, and O-2 and O-4 do not undergo isotopic exchange. The results have important implications for extracting palaeoclimatic records from oxygen isotope time series obtained from tree ring cellulose. As O-5 and O-6 undergo significant exchange with medium water during heterotrophic cellulose synthesis, oxygen isotopes at these positions in tree ring cellulose should carry a predominantly trunk (source) water signal. On the other hand, O-2 and O-4 should retain the isotopic signature of leaf water in tree ring cellulose. Our method therefore potentially enables the separate reconstruction of past temperature and humidity data from oxygen isotope ratios of tree ring cellulose - something that has hitherto not been possible. The measured degrees of isotopic exchange are to some extent unexpected and cannot be fully explained using current biochemical mechanisms, suggesting that knowledge of these processes is incomplete.

  3. Development of a Micropyrolyzer for Enhanced Isotope Ratio Measurement

    SciTech Connect

    Hu, Jianli; Dagle, Robert A.; Johnson, Bradley R.; Kreuzer, Helen W.; Gaspar, Daniel J.; Roberts, Benjamin Q.; Alexander, M. L.

    2008-11-19

    This paper presents design, fabrication and testing of a micro scale reactor for the pyrolysis of organic compounds. The reactor system described here is suitable for use in enhanced isotope ratio measurement in a continuous flow mode. A characteristic of such a system is it can be utilized to pyrolyze organic compounds with sample size 20-50 times smaller than conventional. Results have shown that organic compounds, such as 1-butanol, ethanol, and ethanol amine, can be fully decomposed to desired products CO and H2, at temperature of 1200oC, which is 200oC lower than conventionally reported. Undesired products methane and CO2 are eliminated in the pyrolysis process. The proof-of-concept experimental results clearly demonstrate that the micro pyrolyzer can be readily integrated with isotope ratio mass spectrometer (IRMS) to differentiate between different sources of the same materials.

  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. 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

  6. Measurement of Absolute Carbon Isotope Ratios: Mechanisms and Implications

    NASA Astrophysics Data System (ADS)

    Vogel, J. S.; Giacomo, J. A.; Dueker, S. R.

    2012-12-01

    An accelerator mass spectrometer (AMS) produced absolute isotope ratio measurements for 14C/13C as tested against >500 samples of NIST SRM-4990-C (OxII 14C standard) to an accuracy of 2.2±0.6‰ over a period of one year with measurements made to 1% counting statistics. The spectrometer is not maximized for 13C/12C, but measured ∂13C to 0.4±0.1‰ accuracy, with known methods for improvement. An AMS produces elemental anions from a sputter ion source and includes a charge-changing collision in a gas cell to isolate the rare 14C from the common isotopes and molecular isobars. Both these physical processes have been modeled to determine the parameters providing such absolute measures. Neutral resonant ionization in a cesium plasma produces mass-independent ionization, while velocity dependent charge-state distributions in gas collisions produce relative ion beam intensities that are linear in mass at specific collision energies. The mechanisms are not specific to carbon isotopes, but stand alone absolute IRMS (AIR-MS) instruments have not yet been made. Aside from the obvious applications in metrology, AIR-MS is particularly valuable in coupled separatory MS because no internal or external standards are required. Sample definition processes can be compared, even if no exact standard reference sample exists. Isotope dilution measurements do not require standards matching the dilution end-points and can be made over an extended, even extrapolated, range.

  7. Exploring antimony isotope ratio variations for provenancing purposes

    NASA Astrophysics Data System (ADS)

    Lobo, L.; Degryse, P.; Vanhaecke, F.

    2012-04-01

    Production sites and trade routes of Roman glass have received much attention over the past decade. It is assumed that raw glass was produced in primary workshops near the raw material sources used, to be transported to secondary glass houses. Colourless glass was a particularly prestigious material in this process, difficult to make. It has been looked at from the perspective of the provenance of its sand and flux, but rarely from the perspective of the origin of the decolourizing material. In effect, for the production of early Roman colourless glass, antimony was used, deliberately added under the form of Sb-bearing minerals. Isotopic analysis of Sb ores could help identify the origin of the decolorizing agent present in Roman glasses and, consequently, to reconstruct how such material was traded and transported, and how this can be integrated in the network of primary and secondary glass producers. In this work, variations in the isotopic composition of Sb in different ore sources (stibnites) are explored using multi-collector ICP - mass spectrometry. A new method is proposed, where Sb is directly analysed for its isotopic composition using MC-ICP-MS after chromatographic isolation of the target element from a sample digest. The isotopic composition of the selected materials shows variations up to 6 ?-units relative to an antimony standard solution. Indium was used as internal standard for correction for instrumental mass discrimination and an external precision for the 123Sb/121Sb ratio of 0.01% RSD was obtained

  8. USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory


    We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

  9. TOWARD A UNIQUE NITROGEN ISOTOPIC RATIO IN COMETARY ICES

    SciTech Connect

    Rousselot, Philippe; Cordier, Daniel; Mousis, Olivier; Pirali, Olivier; Vervloet, Michel; Martin-Drumel, Marie-Aline; Gruet, Sébastien; Jehin, Emmanuël; Hutsemékers, Damien; Manfroid, Jean; Arpigny, Claude; Decock, Alice

    2014-01-10

    Determination of the nitrogen isotopic ratios in different bodies of the solar system provides important information regarding the solar system's origin. We unambiguously identified emission lines in comets due to the {sup 15}NH{sub 2} radical produced by the photodissociation of {sup 15}NH{sub 3}. Analysis of our data has permitted us to measure the {sup 14}N/{sup 15}N isotopic ratio in comets for a molecule carrying the amine (-NH) functional group. This ratio, within the error, appears similar to that measured in comets in the HCN molecule and the CN radical, and lower than the protosolar value, suggesting that N{sub 2} and NH{sub 3} result from the separation of nitrogen into two distinct reservoirs in the solar nebula. This ratio also appears similar to that measured in Titan's atmospheric N{sub 2}, supporting the hypothesis that, if the latter is representative of its primordial value in NH{sub 3}, these bodies were assembled from building blocks sharing a common formation location.

  10. Detailed Distribution of the Helium Isotope Ratios in Northeastern Japan

    NASA Astrophysics Data System (ADS)

    Horiguchi, K.; Ueki, S.; Sano, Y.; Takahata, N.; Hasegawa, A.

    2007-12-01

    The geographical distribution of helium isotope ratios (3He/4He ratios) is characterized by high values of 4 to 8RA (where RA is the atmospheric 3He/4He ratio of 1.39×10-6) along the volcanic front and in the back-arc region at Tohoku district, northeastern Japan. In contrast forearc region shows low values less than 1RA. On the other hand, there is no clear contrast of the 3He/4He ratios except at the central region (e.g., Sano and Wakita, 1985). We perform the helium isotope ratio analysis in northeastern Japan, and around the source region of the Niigataken Chuetsu-oki Earthquake in 2007 (M6.8) where 3He/4He ratios data were reported. We have collected 41 samples of gases from hot springs, mineral springs, and deep wells, distributing mainly in the forearc region at Tohoku district. In addition, we also collected 19 samples of gases from hot springs, volcanoes and natural gas fields around the source region of the Niigataken Chuetsu-oki Earthquake in 2007. We measured 3He/4He ratios by noble gas mass spectrometers (Helix and VG5400) of Ocean Research Institute (ORI), the University of Tokyo. The 4He/20Ne were measured by a quadruple mass spectrometer to evaluate air contamination in the samples. δ13C (CO2) values were measured by using a mass spectrometer (DELTA plus XP) of ORI. Main features of our results for Tohoku region are as follows: 1) The 3He/4He ratios in the forearc region are less than 1RA. 2) The 3He/4He ratios vary along the volcanic front. In Miyagi prefecture [38-39N], the ratios range from 2 to 5 RA. On the other hand, the ratios are less than 1RA in and around the southern boundary of Iwate and Akita prefectures [39-39.5N]. The distribution of 3He/4He ratios in Niigata plans to be discussed by comparing with the well-studied seismotectonics and the structure of the crust and upper mantle.

  11. Measurement of stable carbon isotope ratios of non-methane hydrocarbons and halocarbons

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

    Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the

  12. Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

    PubMed

    Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

    2015-01-01

    Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. PMID:25439590

  13. Protein stable isotope fingerprinting: multidimensional protein chromatography coupled to stable isotope-ratio mass spectrometry.

    PubMed

    Mohr, Wiebke; Tang, Tiantian; Sattin, Sarah R; Bovee, Roderick J; Pearson, Ann

    2014-09-01

    Protein stable isotope fingerprinting (P-SIF) is a method to measure the carbon isotope ratios of whole proteins separated from complex mixtures, including cultures and environmental samples. The goal of P-SIF is to expose the links between taxonomic identity and metabolic function in microbial ecosystems. To accomplish this, two dimensions of chromatography are used in sequence to resolve a sample containing ca. 5-10 mg of mixed proteins into 960 fractions. Each fraction then is split in two aliquots: The first is digested with trypsin for peptide sequencing, while the second has its ratio of (13)C/(12)C (value of δ(13)C) measured in triplicate using an isotope-ratio mass spectrometer interfaced with a spooling wire microcombustion device. Data from cultured species show that bacteria have a narrow distribution of protein δ(13)C values within individual taxa (±0.7-1.2‰, 1σ). This is moderately larger than the mean precision of the triplicate isotope measurements (±0.5‰, 1σ) and may reflect heterogeneous distribution of (13)C among the amino acids. When cells from different species are mixed together prior to protein extraction and separation, the results can predict accurately (to within ±1σ) the δ(13)C values of the original taxa. The number of data points required for this endmember prediction is ≥20/taxon, yielding a theoretical resolution of ca. 10 taxonomic units/sample. Such resolution should be useful to determine the overall trophic breadth of mixed microbial ecosystems. Although we utilize P-SIF to measure natural isotope ratios, it also could be combined with experiments that incorporate stable isotope labeling. PMID:25121924

  14. Progress in AMS measurement of U isotope ratios in nanogram U samples

    NASA Astrophysics Data System (ADS)

    Dong, Kejun; He, Ming; Wang, Chen; Zhao, Xinhong; Li, Lili; Zhao, Yonggang; Wang, Xianggao; Shen, Hongtao; Wang, Xiaoming; Pang, Fangfang; Xu, Yongning; Zhao, Qingzhang; Dou, Liang; Yang, Xuran; Wu, Shaoyong; Lin, Deyu; Li, Kangning; You, Qubo; Bao, Yiwen; Hu, Yueming; Xia, Qingliang; Yin, Xinyi; Jiang, Shan

    2015-10-01

    The determination of uranium isotopic composition in ultra-trace U samples is very important in different fields, especially for the nuclear forensics. A new Accelerator Mass Spectrometry (AMS) technique has been developed for the measurement of uranium isotopic ratios in ng level uranium samples at China Institute of Atomic Energy (CIAE). Recently, the method was further optimized and developed by using a series of blank and standard samples. The results show that the 236U at the femtogram level can be determined in nanogram U samples by the newly developed AMS technique at CIAE. The experimental setup, performances and results will be detailed in this contribution.

  15. Potential uses of lead isotope ratios in gunshot cases.

    PubMed

    Keisch, B; Callahan, R C

    1978-05-01

    The determination of lead isotope ratios in 14 bullets, and in material taken from 9 hand swabs and 5 primers shows that there are potentially valuable forensic uses for such a method. While a more complete study is required, this method could possibly be used to prove (or disprove) relatiohships between bullets and manufacturers, weapons, or persons firing the weapons. Sample size requirements (1 microgram or less) are such that damaged or fragmented bullets, or minute particles therefrom, may be used for the required analyses. An experiment showed that gunshot residue from a test-fired weapon was detectable even after washing the hands. PMID:649545

  16. Carbon isotope ratios and isotopic correlations between components in fruit juices

    NASA Astrophysics Data System (ADS)

    Wierzchnicki, Ryszard

    2013-04-01

    Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

  17. Isotopic Ratio Outlier Analysis Global Metabolomics of Caenorhabditis elegans

    PubMed Central

    Szewc, Mark A.; Garrett, Timothy; Menger, Robert F.; Yost, Richard A.; Beecher, Chris; Edison, Arthur S.

    2014-01-01

    We demonstrate the global metabolic analysis of Caenorhabditis elegans stress responses using a mass spectrometry-based technique called Isotopic Ratio Outlier Analysis (IROA). In an IROA protocol, control and experimental samples are isotopically labeled with 95% and 5% 13C, and the two sample populations are mixed together for uniform extraction, sample preparation, and LC-MS analysis. This labeling strategy provides several advantages over conventional approaches: 1) compounds arising from biosynthesis are easily distinguished from artifacts, 2) errors from sample extraction and preparation are minimized because the control and experiment are combined into a single sample, 3) measurement of both the molecular weight and the exact number of carbon atoms in each molecule provides extremely accurate molecular formulae, and 4) relative concentrations of all metabolites are easily determined. A heat shock perturbation was conducted on C. elegans to demonstrate this approach. We identified many compounds that significantly changed upon heat shock, including several from the purine metabolism pathway, which we use to demonstrate the approach. The metabolomic response information by IROA may be interpreted in the context of a wealth of genetic and proteomic information available for C. elegans. Furthermore, the IROA protocol can be applied to any organism that can be isotopically labeled, making it a powerful new tool in a global metabolomics pipeline. PMID:24274725

  18. Crystallization kinetics of rhyolitic melts using oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Befus, Kenneth S.

    2016-01-01

    Crystals provide the means to understand igneous systems, but natural constraints on crystallization kinetics are rare because thermal conditions and crystallization timescales are typically unknown. Oxygen isotope ratios in quartz and alkali feldspar crystals in spherulites provide a natural record of the temperature interval of crystallization and crystal growth rates in rhyolitic melts. Oxygen isotope compositions in both phases change progressively with position from the spherulite core to rim. Quartz δ18O increases from 5.0 ± 0.3‰ in the core to 5.6 ± 0.3‰ at the rims, whereas alkali feldspar decreases from 3.7 ± 0.4‰ in the core to 2.7 ± 0.9‰ at the rims. Fractionation therefore increases from 1.3 ± 0.7‰ in the cores to 2.9 ± 1.1‰ at the rims. Oxygen isotope thermometry tracks crystallization temperature with position. Spherulites nucleate at 578 ± 160°C and continue to grow until 301 ± 88°C. The in situ analyses demonstrate that spherulites self-contain a record of their thermal history and that of the host lava.

  19. Isotope ratio monitoring of small molecules and macromolecules by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Godin, Jean-Philippe; Hau, Jörg; Fay, Laurent-Bernard; Hopfgartner, Gérard

    2005-01-01

    In the field of isotope ratio mass spectrometry, the introduction of an interface allowing the connection of liquid chromatography (LC) and isotope ratio mass spectrometry (IRMS) has opened a range of new perspectives. The LC interface is based on a chemical oxidation, producing CO2 from organic molecules. While first results were obtained from the analysis of low molecular weight compounds, the application of compound-specific isotope analysis by irm-LC/MS to other molecules, in particular biomolecules, is presented here. The influence of the LC flow rate on the CO2 signal and on the observed delta13C values is demonstrated. The limits of quantification for angiotensin III and for leucine were 100 and 38 pmol, respectively, with a standard deviation of the delta13C values better than 0.4 per thousand. Also, accuracy and precision of delta13C values for elemental analyser-IRMS and flow injection analysis-IRMS (FIA-LC/MS) were compared. For compounds with molecular weights ranging from 131 to 66,390 Da, precision was better than 0.3 per thousand, and accuracy varied from 0.1 to 0.7 per thousand. In a second part of the work, a two-dimensional (2D)-LC method for the separation of 15 underivatised amino acids is demonstrated; the precision of delta13C values for several amino acids by irm-LC/MS was better than 0.3 per thousand at natural abundance. For labelled mixtures, the coefficient of variation was between 1% at 0.07 atom % excess (APE) for threonine and alanine, and around 10% at 0.03 APE for valine and phenylalanine. The application of irm-LC/MS to the determination of the isotopic enrichment of 13C-threonine in an extract of rat colon mucosa demonstrated a precision of 0.5 per thousand, or 0.001 atom %. PMID:16124031

  20. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1

  1. Carbon isotope ratios and impurities in diamonds from Southern Africa

    NASA Astrophysics Data System (ADS)

    Kidane, Abiel; Koch-Müller, Monika; Morales, Luiz; Wiedenbeck, Michael; De Wit, Maarten

    2015-04-01

    We are investigating the sources of diamonds from southern Africa by studying both their carbon isotopic composition and chemical impurities. Our samples include macro-sized diamonds from River Ranch kimberlite in Zimbabwe and the Helam and Klipspringer kimberlitic deposits from South Africa, as well as micro-sized diamonds from Klipspringer and Premier kimberlites in South Africa. We have characterized the samples for their structurally bounded nitrogen, hydrogen and platelets defect using a Fourier Transmission Infrared Spectroscopy (FTIR). Using the DiaMap routine, open source software (Howell et al., 2012), IR spectra were deconvulated and quantified for their nitrogen (A, B and D components) and hydrogen contents. High to moderate nitrogen concentrations (1810 to 400 µg/g; 400 to 50 µg/g respectively) were found in diamonds from Klipspringer and Helam. Moderate to low (<50 µg/g) nitrogen concentrations were observed in diamonds from Premier and River Ranch. Type II diamonds, i.e. diamonds with no N impurities, which are presumed to have been derived from ultramafic sources, are found in the River Ranch deposit. The macro- and micro-size diamonds from the Klipspringer deposit display similar nitrogen defects, with higher nitrogen concentration and more frequent D components found in the macro-size diamonds. One of the first steps towards reliable carbon isotope studies is the development of calibration materials for SIMS carbon isotopic analyses. We have investigated candidate materials both from a polycrystalline synthetic diamond sheet and two natural gem quality diamonds from Juina (Brazil). Electron-based images of the synthetic diamond sheet, obtained using GFZ Potsdam's dual beam FIB instrument, show many diamond grains with diameters greater than 35 µm. SIMS testing of the isotopic homogeneity of the back and front sides of the synthetic sheets reveal similar 13C/12C ratio within a RSD of <1 ‰ . SIMS isotopic analyses of the two natural diamond RMs

  2. Last Glacial Maximum and deglacial abyssal seawater oxygen isotopic ratios

    NASA Astrophysics Data System (ADS)

    Wunsch, Carl

    2016-06-01

    An earlier analysis of pore-water salinity (chlorinity) in two deep-sea cores, using terminal constraint methods of control theory, concluded that although a salinity amplification in the abyss was possible during the LGM, it was not required by the data. Here the same methodology is applied to δ18Ow in the upper 100 m of four deep-sea cores. An ice volume amplification to the isotopic ratio is, again, consistent with the data but not required by it. In particular, results are very sensitive, with conventional diffusion values, to the assumed initial conditions at -100 ky and a long list of noise (uncertainty) assumptions. If the calcite values of δ18O are fully reliable, then published enriched values of the ratio in seawater are necessary to preclude sub-freezing temperatures, but the seawater δ18O in pore fluids does not independently require the conclusion.

  3. Improving the Sensitivity of Uranium Isotope Ratio Measurements

    NASA Astrophysics Data System (ADS)

    Friedrich, J.; Snow, J.

    2003-12-01

    Accurate and precise measurements of natural and anthropogenic 235/238 U isotope ratios are important for a range of investigations where the amount of sample is extremely restricted and/or the analyte is only present in ultra-trace quantities. Examples include biological, cosmochemical, environmental, geological, and radiological studies. We have developed and validated a novel method using our Nu Instruments Nu Plasma Multi Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS) and a 233U, 236U mixed double spike for the measurement of 235U/238U ratios. Our multi-dynamic technique employs the installed quadrupole zoom optics and fixed positioning of the ion counting detectors such that rather than the commonly used mass dispersion of 1 or 2, we utilize a mass dispersion of 1.5. Using this configuration, we can simultaneously monitor the 235U and 238U ion beams in the first cycle followed by a second cycle that simultaneously monitors the 233U and 236U beams. This innovative approach allows us to correct for the considerable, but consistent, instrumental mass fractionation and ion-counter amplification bias within each sequence. Since we were hesitant to use a U500 (235U, 238U equal atom) solution for spike calibration because of possible enriched U laboratory and instrumentation contamination, we used a U960 (terrestrial 235U/238U) solution for isotopic calibration of the spike. This standardization corrected for the small amounts of 235U and 238U in the spike solution by using a U960 standard solution. With a mean intraday 2-sigma precision of 1.5 permil and an overall 2-sigma precision of 2.25 permil using individual sample sizes of 350 pg (8.8 x10 E11 atoms), we are confident our technique will be useful for identifying U isotopic anomalies present in many sample types.

  4. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1

  5. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric PM

    NASA Astrophysics Data System (ADS)

    Moukhtar, S.; Saccon, M.; Kornilova, A.; Irei, S.; Huang, L.; Rudolph, J.

    2011-05-01

    A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter (PM) is presented. It has been found in numerous laboratory studies that these compounds are photooxidation products of toluene in PM. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. PM was collected on quartz fibre filters using dichotomous high volume air samplers for PM 2.5. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography (HPLC) and solid phase extraction (SPE). The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyl)trifluoroacetamide (BSTFA), was added to the solution for Gas Chromatography/Mass Spectroscopy (GC/MS) analysis. The second half of the sample was stored at low temperature. When GC/MS analysis showed high enough concentrations the remaining sample was derivatized with BSTFA and analysed for stable isotope ratio using a Gas Chromatography/Isotope Ratio Mass Spectrometry (GC-IRMS). In all atmospheric PM samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol. Nevertheless, due to low pollution levels occurring in the rural area, no samples had concentrations high enough to perform stable carbon isotope composition measurements of the methylnitrophenols. Samples collected in the suburban area could be analysed for carbon stable isotope ratio using GC-IRMS. The procedure described in this paper provides a very sensitive and selective method for the analysis of methylnitrophenols in atmospheric PM at concentrations as low as 1 pg m-3. For accurate (within ±0.5‰) stable isotope ratio analysis significantly higher concentrations in the range of 100 pg m-3 or more are required.

  6. Childhood lead exposure in an industrial town in China: coupling stable isotope ratios with bioaccessible lead.

    PubMed

    Li, Hong-Bo; Chen, Kai; Juhasz, Albert L; Huang, Lei; Ma, Lena Q

    2015-04-21

    Fingerprinting based on stable isotopes of lead (Pb) in blood and environmental media helps to identify Pb exposure pathways in children. However, previous studies used stable isotopes of total Pb in media. In this study, a wire rope production town in China (Zhuhang) was selected for investigating the effectiveness of using isotope ratios in bioaccessible Pb to identify childhood Pb exposure pathways. Blood Pb levels of 115 children in Zhuhang were 1.7-20.4 μg dL(-1), averaging 6.1 ± 3.2 μg dL(-1) (mean ± standard deviation), and were ∼1.6 times the national average in China (3.9 ± 1.8 μg dL(-1)). Among different environmental media (housedust, soil, PM10, vegetables, rice, and drinking water), housedust (695 ± 495 mg kg(-1)) and vegetables [0.36 ± 0.40 mg (kg of fresh weight)(-1)] contained elevated Pb concentrations. The isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb) of total Pb were the highest in housedust (0.8587 ± 0.0039 and 2.1049 ± 0.0087) but lower than blood Pb ratios (0.8634 ± 0.0027 and 2.1244 ± 0.0061). When using bioaccessible Pb in housedust (0.8639 ± 0.0018 and 2.1171 ± 0.0036), the isotope ratios overlapped with blood Pb ratios, suggesting that incidental ingestion of housedust was the predominant contributor to children's blood Pb. Coupling the stable isotope technique with bioaccessible Pb is more reliable for identifying Pb exposure pathways than total Pb determinations. PMID:25803404

  7. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    NASA Astrophysics Data System (ADS)

    Annewandter, R.

    2013-12-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced soil gas sampling during On-Site inspections. Gas transport has been widely studied with different numerical codes. However, gas transport of all radioxenons in the post-detonation regime and their possible fractionation is still neglected in the open literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radioxenons, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different diffusivities due to mass differences between the radioxenons. A previous study showed surface arrival time of a chemically inert gaseous tracer is affected by its diffusivity. They observed detectable amount for SF6 50 days after detonation and 375 days for He-3. They predict 50 and 80 days for Xe-133 and Ar-37 respectively. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations , fracture propagation in fractured, porous media, Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic

  8. Activities of Pu and Am isotopes and isotopic ratios in a soil contaminated by weapons-grade plutonium.

    PubMed

    Lee, M H; Clark, S B

    2005-08-01

    An accident and fire at the former McGuire Air Force Base and Boeing Michigan Aeronautical Research Center (BOMARC) site in New Jersey resulted in dispersion of weapons-grade plutonium in particulate form to the local environment. Soil samples collected at the BOMARC site were measured for their activities and isotopic ratios of Pu and Am isotopes by radioanalytical techniques. The activities of the Pu and Am isotopes in the BOMARC soil were markedly higher than fallout levels, and they decreased nearly exponentially with increasing particle size of the soil. The measured (241)Am activity was compared to calculated values based on decay of (241)Pu. The activity ratios of (238)Pu/(239,240)Pu, (241)Pu/(239,240)Pu, and (241)Am/(239,240)Pu observed in the BOMARC soil were much lower than those attributed to nuclear reprocessing plants and Chernobyl fallout. From the activity ratios of (241)Pu/(239,240)Pu and (241)Am/(239,240)Pu, the origin of the Pu isotopes was identified as weapons-grade and the time since production of the material was estimated. Furthermore, the atomic ratio of (240)Pu/(239)Pu in the BOMARC soil was remarkably lower than the fallout value influenced by nuclear weapons testing and the Chernobyl accident. The atomic ratio of (240)Pu/(239)Pu was very close to the value of the weapons-grade Pu detected from the Thule accident in Greenland. This work demonstrates the utility of radioanalytical measurements and decay calculations for defining characteristics of the source term and discriminating multiple processes that contribute to a source. Such an approach would also be needed to respond to a terrorist event involving an improvised nuclear device or radiological dispersal device. PMID:16124281

  9. Isomer ratio calculations using modeled discrete levels

    SciTech Connect

    Gardner, M.A.; Gardner, D.G.; Hoff, R.W.

    1984-10-16

    Isomer ratio calculations were made for the reactions: /sup 175/Lu(n,..gamma..)/sup 176m,g/Lu, /sup 175/Lu(n,2n)/sup 174m,g/Lu, /sup 237/Np(n,2n)/sup 236m,g/Np, /sup 241/Am(n,..gamma..)/sup 242m,g/Am, and /sup 243/Am(n,..gamma..)/sup 244m,g/Am using modeled level structures in the deformed, odd-odd product nuclei. The hundreds of discrete levels and their gamma-ray branching ratios provided by the modeling are necessary to achieve agreement with experiment. Many rotational bands must be included in order to obtain a sufficiently representative selection of K quantum numbers. The levels of each band must be extended to appropriately high values of angular momentum.

  10. Precise determination of stable chlorine isotopic ratios in low-concentration natural samples

    NASA Astrophysics Data System (ADS)

    Magenheim, A. J.; Spivack, A. J.; Volpe, C.; Ransom, B.

    1994-07-01

    Investigation of stable chlorine isotopes in geological materials has been hindered by large sample requirements and/or lack of analytical precision. Here we describe precise methods for the extraction, isolation, and isotopic analysis of low levels of chlorine in both silicate and aerosol samples. Our standard procedure uses 2 μg of Cl for each isotopic analysis. External reproducibility (1 σ) is 0.25%. for the 37Cl /35Cl measurements. Chlorine is extracted from silicate samples (typically containing at least 20 μg of Cl) via pyrohydrolysis using induction heating and water vapor as the carrier, and the volatilized chlorine is condensed in aqueous solution. Atmospheric aerosols collected on filters are simply dissolved in water. Prior to isotopic measurement, removal of high levels of SO 42-, F -, and organic compounds is necessary for the production of stable ion beams. Sulfate is removed by BaSCO 4 precipitation, F - by CaF 2 precipitation, and organic compounds are extracted with activated carbon. Chlorine is converted to stoichiometric CsCl by cation exchange, and isotopic ratios are determined by thermal ionization mass spectrometry of Cs 2Cl +. We demonstrate that the sensitivity and precision of this method allow resolution of natural variations in chlorine isotopic composition, and thereby provide insight to some fundamental aspects of chlorine geochemistry.

  11. Sulfur isotopic ratio of DMS and DMSP from Lake Kinneret

    NASA Astrophysics Data System (ADS)

    Sela-Adler, Michal; Said-Ahmad, Ward; Eckert, Werner; Kamyshny, Alexey; Sivan, Orit; Amrani, Alon

    2014-05-01

    Volatile Organic sulfur compounds (VOSC) such as dimethylsulfide (DMS) are an important source of biogenic sulfur to the atmosphere. The main precursor of DMS is dimethylsulfoniopropionate (DMSP), a common osmolyte in marine algae. Atmospheric release of VOS compounds contributes to the formation of sulfate aerosols. The latter are of global importance due to their role as cloud-condensation nuclei. VOSC are abundant in terrestrial environments as well and may be involved in important biogeochemical cycles. In lake sediments, another mechanism for the formation of DMS by H2S methylation may be important. The 34S/32S ratio (d34S values) of DMSP of marine surface water around the globe is very homogeneous ranging between +18.9 o to +20.3 o and the fractionation between DMSP and DMS is < +1 o (Amrani et al. 2013). The δ34S values of DMS and other VOSC in sediments should be 34S depleted, similar to its H2S precursor (Oduro et al., 2011). Our goal was to quantify the benthic DMS and DMSP emissions from the sediments of warm monomictic Lake Kinneret relative to their formation by surface water algae by using sulfur isotope ratios. Water column samples and sediment samples from Lake Kinneret were purged and trap in order to extract the VOSC and then introduced to a GC/MC-ICPMS for isotopic measurements (Amrani et al. 2013). The δ34S of DMSP in the water and sediment columns of Lake Kinneret a mesotrophic monomictic lake were measured. Our preliminary results show δ34S values for DMSP ranged between +10.3 o and +13.4 o in the water column. The sulfate δ34S values ranged between +12.6 o to +14.9 o. δ34S -DMSP in the sediment column showed similar values between +9.4 o and +13.0 o, indicating a similar sulfur source. Similar δ34S values obtain for other VOSC such as ethanethiol that contributes significantly to the VOSC of Lake Kinneret sediments. Amrani, A., W. Said-Ahmad,Y. Shaked, and R. P. Kiene. 2013. Sulfur isotopes homogeneity of oceanic DMSP and DMS. PNAS 110

  12. Tracing contamination sources in soils with Cu and Zn isotopic ratios.

    PubMed

    Fekiacova, Z; Cornu, S; Pichat, S

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. PMID:25723961

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  14. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    NASA Astrophysics Data System (ADS)

    Annewandter, Robert

    2014-05-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced gas transport and subsequent soil gas sampling during On-Site inspections. Generally, gas transport has been widely studied with different numerical codes. However, gas transport of radioxenons and radioiodines in the post-detonation regime and their possible fractionation is still neglected in the open peer-reviewed literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the multiple isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radionuclides, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different mass diffusivities due to mass differences between the radionuclides. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures or highly conductive faults which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a so-called ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which is recognized by the oil industry as leading in Discrete Fracture-Matrix (DFM) simulations. It has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations, fracture propagation in fractured, porous media, and Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic differential equations by a complementary finite

  15. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    NASA Astrophysics Data System (ADS)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration–rotation first and second-overtone CO lines in 1.5–2.5 μm spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M ⊙ and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of 16O/17O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2–2 M ⊙ stars after the first dredge-up. In contrast, the 16O/18O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the 16O/18O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected

  16. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

    NASA Astrophysics Data System (ADS)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian

    2009-10-01

    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  17. Nitrogen isotopic ratios in fecal pellets produced by marine zooplankton

    SciTech Connect

    Altabet, M.A. ); Small, L.F. )

    1990-01-01

    At each site and in every season studied, zooplankton in the upper ocean produced fecal pellets that were 1.3% lower in {delta}{sup 15}N than their body tissue but 2.2% higher than their apparent food source. {sup 14}N-containing molecules are evidently preferentially assimilated in zooplankton intestinal tracts, though other isotopic effects must account for the enrichment in {sup 15}N of these organisms relative to their food. These results also show zooplankton to be important modifiers of nitrogen isotopic ratios for marine particulate matter. {delta}{sup 15}N values for sinking particles and fecal pellets are similar, supporting the perspective that macrozooplankton are important factors in producing and processing particles that sink into the ocean's interior and sediments. In contrast, the relationship in {delta}{sup 15}N between fecal pellets and suspended particles in the euphotic zone is more variable. It appears that zooplankton select food particles of varying {delta}{sup 15}N from the suspended particle pool. These results suggest that both zooplankton feeding behavior and their digestive chemistry are important in determining the composition of sinking particulate matter in the ocean with respect to the suspended particle source in the euphotic zone.

  18. A New Multi Collector Isotope Ratio Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Appelhans, A. D.; Olson, J. E.; Ward, M. B.; Dahl, D. A.

    2007-12-01

    With the goal of improving the sensitivity of isotope ratio measurements, particularly for actinides, a new magnetic sector mass spectrometer that utilizes up to seven full-sized discrete dynode electron multipliers operating simultaneously has been designed, constructed and is in the early stages of testing. The design is based on a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated by 35 mm; this allows a full-sized discrete dynode pulse counting multiplier to be used for each beam. The ion dispersion lens (US patents 6,297,501 and pending) is a two element electrostatic 90 degree sector device that causes the beam-to-beam dispersion to increase faster than the intra-beam dispersion. Each of the multipliers is housed in an isolated case and is equipped with a deflector/condenser lens at the entrance to optimize pulse generation. The instrument includes a 9-sample filament cartridge mounted on a micro-manipulator X-Y stage that enables adjustment of the filament position with 10 micron resolution within the ion lens. Initial testing has shown that the instrument is performing as predicted by the ion optics model of the design.

  19. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    NASA Astrophysics Data System (ADS)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  20. Water isotopic ratios from a continuously melted ice core sample

    NASA Astrophysics Data System (ADS)

    Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Kettner, E.; Johnsen, S. J.

    2011-11-01

    A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW-SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present

  1. Estimation of boron isotope ratios using high resolution continuum source atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Wiltsche, Helmar; Prattes, Karl; Zischka, Michael; Knapp, Günter

    2009-04-01

    In the production of 10B enriched steels, the production-recycling process needs to be closely monitored for inadvertent mix-up of materials with different B isotope levels. A quick and simple method for the estimation of boron isotope ratios in high alloyed steels using high resolution continuum source flame AAS (HR-CS-FAAS) was developed. On the 208.9 nm B line the wavelength of the peak absorption of 10B and 11B differs by 2.5 pm. The wavelength of the peak absorption of boron was determined by fitting a Gauss function through spectra simultaneously recorded by HR-CS-FAAS. It was shown that a linear correlation between the wavelength of the peak absorption and the isotope ratio exists and that this correlation is independent of the total boron concentration. Internal spectroscopic standards were used to compensate for monochromator drift and monochromator resolution changes. Accuracy and precision of the analyzed samples were thereby increased by a factor of up to 1.3. Three steel reference materials and one boric acid CRM, each certified for the boron isotope ratio were used to validate the procedure.

  2. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  3. Titan's Carbon Isotopic Ratio: A Clue To Atmospheric Evolution?

    NASA Astrophysics Data System (ADS)

    Nixon, C. A.; Jennings, D. E.; Romani, P. N.; Jolly, A.; Teanby, N. A.; Irwin, P. G.; Bézard, B.; Vinatier, S.; Coustenis, A.; Flasar, F. M.

    2009-12-01

    In this presentation we describe the latest results to come from Cassini CIRS and ground-based telescopic measurements of Titan's 12C/13C ratio in atmospheric molecules, focusing on hydrocarbons. Previously, the Huygens GCMS instrument measured 12CH4/13CH4 to be 82±1 (Niemann et al., Nature, 438, 779-784, 2005), substantially and significantly lower than the VPDB inorganic Earth standard of 89.4. It is also at odds with measurements for the giant planets. Cassini CIRS infrared spectra have confirmed this enhancement in 13CH4, but also revealed that the ratio in ethane, the major photochemical product of methane photolysis, does not appear enhanced (90±7) (Nixon et al.. Icarus, 195, 778-791, 2008) and is compatible with the terrestrial and combined giant planet value (88±7, Sada et al., Ap. J., 472, p. 903-907, 1996). Recently-published results from spectroscopy using the McMath-Pierce telescope at Kitt Pitt (Jennings et al., JCP, 2009, in press) have confirmed this deviation between methane and ethane, and an explanation has been proposed. This invokes a kinetic isotope effect (KIE) in the abstraction of methane by ethynyl, a major ethane formation pathway, to preferentially partition 12C into ethane and leave an enhancement in atmospheric 13CH4 relative to the incoming flux from the reservoir. Modeling shows that a steady-state solution exists where the 12C/13C methane is decreased from the reservoir value by exactly the KIE factor (the ratio of 12CH4 to 13CH4 abstraction reaction rates): which is plausibly around 1.08, very close to the observed amount. However, a second solution exists in which we are observing Titan about ~1 methane lifetime after a major injection of methane into the atmosphere which is rapidly being eliminated. Updated measurements by Cassini CIRS of both the methane and ethane 12C/13C ratios will be presented, along with progress in interpreting this ratio. In addition, we summarize the 12C/13C measurements by CIRS in multiple other Titan

  4. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    Zhao, Liangju; Xiao, Honglang; Zhou, Jian; Wang, Lixin; Cheng, Guodong; Zhou, Maoxian; Yin, Li; McCabe, Matthew F

    2011-10-30

    As an alternative to isotope ratio mass spectrometry (IRMS), the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and the capacity for field-based application for the analysis of the stable isotopes of water. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in incorrect results for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every 2 h for 24-48 h) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic compositions of the extracted water from these samples were measured using both an IRMS and an IRIS instrument. The results show that the mean discrepancies between the IRMS and IRIS approaches for δ(18) O and δD, respectively, were: -5.6‰ and -75.7‰ for leaf water; -4.0‰ and -23.3‰ for stem water; -3.4‰ and -28.2‰ for root water; -0.5‰ and -6.7‰ for xylem water; -0.06‰ and -0.3‰ for xylem flow; and -0.1‰ and 0.3‰ for soil water. The order of the discrepancy was: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling at nighttime did not remove the observed deviations. PMID:21953962

  5. Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Xiao, H.; Zhou, J.; Wang, L.; Cheng, G.; Zhou, M.; Yin, L.; McCabe, M. F.

    2011-12-01

    As an alternative to isotope ratio mass spectrometry (IRMS) the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and capacity for field based application for the analysis of stable water isotopes. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in errant readings for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every two hours for 24-48 hours) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic composition of the extracted water from these samples was measured using both an IRMS and IRIS instrument. Results show that the mean discrepancy between the IRMS and IRIS approach, for δ18O and δD respectively, was: -5.6% and -75.7% for leaf water; -4.0% and -23.3% for stem water; -3.4% and -28.2% for root water; -6.7% and -0.5% for xylem water; -0.06% and -0.3% for xylem flow; and -0.1% and 0.3% for soil water. The order of the discrepancy followed: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling during the nighttime did not remove the observed deviations.

  6. 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.

  7. Late Miocene evolution of the Black Sea: insights from palynology and strontium isotope ratios

    NASA Astrophysics Data System (ADS)

    Grothe, Arjen; van Baak, Christiaan; Vasiliev, Iuliana; Sangiorgi, Francesca; Reichart, Gert-Jan; Stoica, Marius; Krijgsman, Wout

    2016-04-01

    During the late Miocene, the connection(s) between the Mediterranean Basin and the Atlantic Ocean deteriorated, which ultimately culminated in thick evaporite deposits and a water level drop in the Mediterranean Basin during the so-called Messinian Salinity Crisis (MSC, 5.97 - 5.33 Ma). It has been claimed that Black Sea, in response to the MSC, also desiccated but these claims have been proven incorrectly. Here we present palynological (dinoflagellate cysts and pollen) and strontium isotope ratios from two Black Sea records: the Zheleznyi Rog outcrop section and Deep Sea Drilling Project Hole 380A. Organic walled cyst-producing dinoflagellates are highly sensitive to even small changes in surface waters and strontium isotope ratios are excellent recorders of changing connectivity. Our records provide therefore more insights in the sensitivity of the Black Sea to Messinian Salinity Crisis and the general evolution of the late Miocene Black Sea.

  8. 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

  9. Effects of carbonate leaching on foraminifer stable isotopes ratios

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  10. Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.

    PubMed

    West, Adam G; Goldsmith, Gregory R; Brooks, Paul D; Dawson, Todd E

    2010-07-30

    The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46 per thousand (delta(2)H) and 15.4 per thousand (delta(18)O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35 per thousand (delta(2)H) and 11.8 per thousand (delta(18)O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument-based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS. PMID:20552579

  11. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae: Implications for palaeoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Brett, Marianne J.; Baldini, James U. L.; Gröcke, Darren R.

    2014-09-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand model. The dominant influence on stable isotope ratios within the majority of Podocarpaceae studied here is vapour pressure deficit (VPD). A simple latitudinal trend does not exist, and neither temperature nor rainfall (decoupled from VPD) controls the stable isotope ratios. The results suggest that modern spatial heterogeneity in VPD affects the stable isotope values of vegetation, and that historic VPD variability would change the stable isotope ratios of Podocarpaceae without necessitating a change in vegetation type, density, or productivity. This represents an alternative model for temporal isotope change within geochemical proxies and reinforces the need for increased stable isotopic research in modern plant ecosystems to better understand modern, and eventually palaeoclimatic processes affecting the terrestrial biosphere.

  12. Carbon Isotope Ratios Demonstrate Carbon Flux from C4 Host to C3 Parasite 1

    PubMed Central

    Press, Malcolm C.; Shah, Nishith; Tuohy, Janet M.; Stewart, George R.

    1987-01-01

    Carbon isotope ratios of mature leaves from the C3 angiosperm root hemiparasites Striga hermonthica (Del.) Benth (−26.7‰) and S. asiatica (L.) Kuntze (−25.6‰) were more negative than their C4 host, sorghum (Sorghum bicolor [L.] Moench cv CSH1), (−13.5‰). However, in young photosynthetically incompetent plants of S. hermonthica this difference was reduced to less than 1‰. Differences between the carbon isotope ratios of two C3-C3 associations, S. gesnerioides (Willd.) Vatke—Vigna unguiculata (L.) Walp. and Oryza sativa L.—Rhamphicarpa fistulosa (Hochst.) Benth differed by less than 1‰. Theoretical carbon isotope ratios for mature leaves of S. hermonthica and S. asiatica, calculated from foliar gas exchange measurements, were −31.8 and −32.0‰, respectively. This difference between the measured and theoretical δ13C-values of 5 to 6‰ suggests that even in mature, photosynthetically active plants, there is substantial input of carbon from the C4 host. We estimate this to be approximately 28% of the total carbon in S. hermonthica and 35% in S. asiatica. This level of carbon transfer contributes to the host's growth reductions observed in Striga-infected sorghum. PMID:16665818

  13. High-sensitivity measurement of 3He-4He isotopic ratios for ultracold neutron experiments

    NASA Astrophysics Data System (ADS)

    Mumm, H. P.; Huber, M. G.; Bauder, W.; Abrams, N.; Deibel, C. M.; Huffer, C. R.; Huffman, P. R.; Schelhammer, K. W.; Janssens, R.; Jiang, C. L.; Scott, R. H.; Pardo, R. C.; Rehm, K. E.; Vondrasek, R.; Swank, C. M.; O'Shaughnessy, C. M.; Paul, M.; Yang, L.

    2016-06-01

    Research efforts ranging from studies of solid helium to searches for a neutron electric dipole moment require isotopically purified helium with a ratio of 3He to 4He at levels below that which can be measured using traditional mass spectroscopy techniques. We demonstrate an approach to such a measurement using accelerator mass spectroscopy, reaching the 10-14 level of sensitivity, several orders of magnitude more sensitive than other techniques. Measurements of 3He/4He in samples relevant to the measurement of the neutron lifetime indicate the need for substantial corrections. We also argue that there is a clear path forward to sensitivity increases of at least another order of magnitude.

  14. Stable isotope ratio determination of the origin of vanillin in vanilla extracts and its relationship to vanillin/potassium ratios

    SciTech Connect

    Martin, G.E.; Alfonso, F.C.; Figert, D.M.; Burggraff, J.M.

    1981-09-01

    A method is described for isolating vanillin from vanilla extract, followed by stable isotope ratio analysis to determine the amount of natural vanillin contained in adulterated vanilla extracts. After the potassium content is determined, the percent Madagascar and/or Java vanilla beans incorporated into the extract may then be approximated from the vanillin/potassium ratio.

  15. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  16. 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.

  17. 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

  18. Forensic Applications of Light-Element Stable Isotope Ratios of Ricinus communis Seeds and Ricin Preparations

    SciTech Connect

    Kreuzer, Helen W.; West, Jason B.; Ehleringer, James

    2013-01-01

    Seeds of the castor plant Ricinus communis, also known as castor beans, are of forensic interest because they are the source of the poison ricin. We have tested whether stable isotope ratios of castor seeds and ricin prepared by various methods can be used as a forensic signature. We collected over 300 castor seed samples from locations around the world and measured the C, N, O, and H stable isotope ratios of the whole seeds, oil, and three types of ricin preparations. Our results demonstrate that N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pair-wise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  19. 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.

  20. Equations for Lipid Normalization of Carbon Stable Isotope Ratios in Aquatic Bird Eggs

    PubMed Central

    Elliott, Kyle H.; Davis, Mikaela; Elliott, John E.

    2014-01-01

    Stable isotope ratios are biogeochemical tracers that can be used to determine the source of nutrients and contaminants in avian eggs. However, the interpretation of stable carbon ratios in lipid-rich eggs is complicated because 13C is depleted in lipids. Variation in 13C abundance can therefore be obscured by variation in percent lipids. Past attempts to establish an algebraic equation to correct carbon isotope ratios for lipid content in eggs have been unsuccessful, possibly because they relied partly on data from coastal or migratory species that may obtain egg lipids from different habitats than egg protein. We measured carbon, nitrogen and sulphur stable isotope ratios in 175 eggs from eight species of aquatic birds. Carbon, nitrogen and sulphur isotopes were enriched in lipid-extracted egg samples compared with non extracted egg samples. A logarithmic equation using the C∶N ratio and carbon isotope ratio from the non extracted egg tissue calculated 90% of the lipid-extracted carbon isotope ratios within ±0.5‰. Calculating separate equations for eggs laid by species in different habitats (pelagic, offshore and terrestrial-influenced) improved the fit. A logarithmic equation, rather than a linear equation as often used for muscle, was necessary to accurately correct for lipid content because the relatively high lipid content of eggs compared with muscle meant that a linear relationship did not accurately approximate the relationship between percent lipids and the C∶N ratio. Because lipid extraction alters sulphur and nitrogen isotope ratios (and cannot be corrected algebraically), we suggest that isotopic measurement on bulk tissue followed by algebraic lipid normalization of carbon stable isotope ratio is often a good solution for homogenated eggs, at least when it is not possible to complete separate chemical analyses for each isotope. PMID:24465384

  1. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰). PMID:26511394

  2. Concentrations and activity ratios of uranium isotopes in groundwater from Donana National Park, South of Spain

    SciTech Connect

    Bolivar, J. P.; Olias, M.; Gonzalez-Garcia, F.; Garcia-Tenorio, R.

    2008-08-07

    The levels and distribution of natural radionuclides in groundwaters from the unconfined Almonte-Marismas aquifer, upon which Donana National Park is located, have been analysed. Most sampled points were multiple piezometers trying to study the vertical distribution of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, physico-chemical properties, major and minor ions, trace elements and natural radionuclides (U-isotopes, Th-isotopes, Ra-isotopes and {sup 210}Po), were also analysed. In the southern zone, where aeolian sands crop out, water composition is of the sodium chloride type, and the lower U-isotopes concentrations have been obtained. As water circulates through the aquifer, bicarbonate and calcium concentrations increase slightly, and higher radionuclides concentrations were measured. Finally, we have demonstrated that {sup 234}U/{sup 238}U activity ratios can be used as markers of the type of groundwater and bedrock, as it has been the case for old waters with marine origin confined by a marsh in the south-east part of aquifer.

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

    PubMed Central

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

    2016-01-01

    Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538

  4. Reducing and correcting for contamination of ecosystem water stable isotopes measured by isotope ratio infrared spectroscopy.

    PubMed

    Schmidt, Markus; Maseyk, Kadmiel; Lett, Céline; Biron, Philippe; Richard, Patricia; Bariac, Thierry; Seibt, Ulli

    2012-01-30

    Concern exists about the suitability of laser spectroscopic instruments for the measurement of the (18)O/(16)O and (2)H/(1)H values of liquid samples other than pure water. It is possible to derive erroneous isotope values due to optical interference by certain organic compounds, including some commonly present in ecosystem-derived samples such as leaf or soil waters. Here we investigated the reliability of wavelength-scanned cavity ring-down spectroscopy (CRDS) (18)O/(16)O and (2)H/(1)H measurements from a range of ecosystem-derived waters, through comparison with isotope ratio mass spectrometry (IRMS). We tested the residual of the spectral fit S(r) calculated by the CRDS instrument as a means to quantify the difference between the CRDS and IRMS δ-values. There was very good overall agreement between the CRDS and IRMS values for both isotopes, but differences of up to 2.3‰ (δ(18)O values) and 23‰ (δ(2)H values) were observed in leaf water extracts from Citrus limon and Alnus cordata. The S(r) statistic successfully detected contaminated samples. Treatment of Citrus leaf water with activated charcoal reduced, but did not eliminate, δ(2)H(CRDS) - δ(2)H(IRMS) linearly for the tested range of 0-20% charcoal. The effect of distillation temperature on the degree of contamination was large, particularly for δ(2)H values but variable, resulting in positive, negative or no correlation with distillation temperature. S(r) and δ(CRDS) - δ(IRMS) were highly correlated, in particular for δ(2)H values, across the range of samples that we tested, indicating the potential to use this relationship to correct the δ-values of contaminated plant water extracts. We also examined the sensitivity of the CRDS system to changes in the temperature of its operating environment. We found that temperature changes ≥4 °C for δ(18)O values and ≥10 °C for δ(2)H values resulted in errors larger than the CRDS precision for the respective isotopes and advise the use of such

  5. Relationship between carbon and nitrogen isotope ratios for lower trophic ecosystem in marine environments

    NASA Astrophysics Data System (ADS)

    Aita, M. N.; Ishii, R.; Tadokoro, K.; Smith, S. L.; Wada, E.

    2012-12-01

    To examine the relationship between carbon and nitrogen stable isotope ratios (δ13C and δ15N) along food chains, we analyzed using the data from the Oyashio waters at the western North Pacific (samples collected from March to October 2009), the warm-core ring 86-B derived from the Kuroshio extension region (preserved samples), and previously published data from the Gulf of Alaska and Antarctic Ocean. The statistical analysis suggested a common slope of δ15N versus δ13C (Δδ15N/Δδ13C) among regions. We attribute this similarity to common physiological aspects of feeding processes (e.g., kinetic isotope effects inherent in the processes of amino acid synthesis). We also compared seasonal differences seasonal in Δδ15N/Δδ13C for the euphotic layers of the Oyashio waters. The Δδ15N/Δδ13C slope of the food chain during the spring bloom differs from its common value in other seasons. If we could better understand both carbon and nitrogen trophic fractionation within ecosystems, the stable isotope ratios may help to elucidate migratory behavior of higher trophic levels such as fishes in marine ecosystems as well as frame work of biogeochemical cycles in question.

  6. Can stable isotope ratios provide for community-wide measures of trophic structure?

    PubMed

    Layman, Craig A; Arrington, D Albrey; Montaña, Carmen G; Post, David M

    2007-01-01

    Stable isotope ratios (typically of carbon and nitrogen) provide one representation of an organism's trophic niche and are widely used to examine aspects of food web structure. Yet stable isotopes have not been applied to quantitatively characterize community-wide aspects of trophic structure (i.e., at the level of an entire food web). We propose quantitative metrics that can be used to this end, drawing on similar approaches from ecomorphology research. For example, the convex hull area occupied by species in delta13C-delta15N niche space is a representation of the total extent of trophic diversity within a food web, whereas mean nearest neighbor distance among all species pairs is a measure of species packing within trophic niche space. To facilitate discussion of opportunities and limitations of the metrics, we provide empirical and conceptual examples drawn from Bahamian tidal creek food webs. These examples illustrate how this methodology can be used to quantify trophic diversity and trophic redundancy in food webs, as well as to link individual species to characteristics of the food web in which they are embedded. Building from extensive applications of stable isotope ratios by ecologists, the community-wide metrics may provide a new perspective on food web structure, function, and dynamics. PMID:17489452

  7. High-precision (143)Nd/(144)Nd ratios from NdO(+) data corrected with in-run measured oxygen isotope ratios.

    PubMed

    Chu, Zhu-Yin; Li, Chao-Feng; Hegner, Ernst; Chen, Zhi; Yan, Yan; Guo, Jing-Hui

    2014-11-18

    The NdO(+) technique has been considerably refined in recent years for high-precision measurement of Nd isotope ratios in low-level samples (1-5 ng Nd). As oxygen isotopic compositions may vary significantly with experimental conditions such as filament material, ionization enhancer and the ambient oxygen in the ion source, great "care" should be taken for using correct oxygen isotopic compositions to do the isobaric oxide corrections for the "conventional" NdO(+) method. Our method presented here for NdO(+) data reduction and PrO(+) interference corrections uses the oxygen isotope composition determined in each cycle of the NdO(+) measurements. For that purpose, we measured the small ion signals of (150)Nd(17)O(+) and (150)Nd(18)O(+) with amplifiers equipped with 10(12) Ω feedback resistors, and those of Nd(16)O(+) ion beams with 10(11) Ω amplifiers. Using 10(12) Ω amplifiers facilitates a precise measurement of the very small (150)Nd(17)O(+) and (150)Nd(18)O(+) ion signals and calculation of highly accurate and precise (143)Nd/(144)Nd isotope ratios. The (143)Nd/(144)Nd ratios for JNdi-1 standards and several whole-rock reference materials determined with the method on 4 ng of Nd loads are consistent with previously reported values within analytical error, with internal and external precision (2 RSE and 2 RSD) of better than 20 and 30 ppm, respectively. PMID:25301302

  8. Secondary ionization mass spectrometric analysis of impurity element isotope ratios in nuclear reactor materials

    NASA Astrophysics Data System (ADS)

    Gerlach, D. C.; Cliff, J. B.; Hurley, D. E.; Reid, B. D.; Little, W. W.; Meriwether, G. H.; Wickham, A. J.; Simmons, T. A.

    2006-07-01

    During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence and fuel burnup. Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated nuclear reactor graphite. Direct SIMS measurements were made in graphite samples, following shaping and surface cleaning. Models predicting local fuel burnup based on isotopic measurements of B and Li isotopes by SIMS agreed well with U and Pu isotopic measurements obtained by thermal ionization mass spectrometry (TIMS).

  9. Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2010-01-27

    A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed. PMID:20025274

  10. The isotope systematics of a juvenile intraplate volcano: Pb, Nd, and Sr isotope ratios of basalts from Loihi Seamount, Hawaii

    USGS Publications Warehouse

    Staudigel, H.; Zindler, A.; Hart, S.R.; Leslie, T.; Chen, C.-Y.; Clague, D.

    1984-01-01

    Sr, Nd, and Pb isotope ratios for a representative suite of 15 basanites, alkali basalts, transitional basalts and tholeiites from Loihi Seamount, Hawaii, display unusually large variations for a single volcano, but lie within known ranges for Hawaiian basalts. Nd isotope ratios in alkali basalts show the largest relative variation (0.51291-0.51305), and include the nearly constant tholeiite value ( ??? 0.51297). Pb isotope ratios show similarly large ranges for tholeiites and alkali basalts and continue Tatsumoto's [31] "Loa" trend towards higher 206Pb 204Pb ratios, resulting in a substantial overlap with the "Kea" trend. 206Pb 204Pb ratios for Loihi and other volcanoes along the Loa and Kea trends [31] are observed to correlate with the age of the underlying lithosphere suggesting lithosphere involvement in the formation of Hawaiian tholeiites. Loihi lavas display no correlation of Nd, Sr, or Pb isotope ratios with major element compositions or eruptive age, in contrast with observations of some other Hawaiian volcanoes [38]. Isotope data for Loihi, as well as average values for Hawaiian volcanoes, are not adequately explained by previously proposed two-end-member models; new models for the origin and the development of Hawaiian volcanoes must include mixing of at least three geochemically distinct source regions and allow for the involvement of heterogeneous oceanic lithosphere. ?? 1984.

  11. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry

    2000-01-01

    The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  12. The IRHUM (Isotopic Reconstruction of Human Migration) database - bioavailable strontium isotope ratios for geochemical fingerprinting in France

    NASA Astrophysics Data System (ADS)

    Willmes, M.; McMorrow, L.; Kinsley, L.; Armstrong, R.; Aubert, M.; Eggins, S.; Falguères, C.; Maureille, B.; Moffat, I.; Grün, R.

    2013-11-01

    Strontium isotope ratios (87Sr/86Sr) are a key geochemical tracer used in a wide range of fields including archaeology, ecology, food and forensic sciences. These applications are based on the principle that the Sr isotopic ratios of natural materials reflect the sources of strontium available during their formation. A major constraint for current studies is the lack of robust reference maps to evaluate the source of strontium isotope ratios measured in the samples. Here we provide a new dataset of bioavailable Sr isotope ratios for the major geologic units of France, based on plant and soil samples (Pangaea data repository doi:10.1594/PANGAEA.819142). The IRHUM (Isotopic Reconstruction of Human Migration) database is a web platform to access, explore and map our dataset. The database provides the spatial context and metadata for each sample, allowing the user to evaluate the suitability of the sample for their specific study. In addition, it allows users to upload and share their own datasets and data products, which will enhance collaboration across the different research fields. This article describes the sampling and analytical methods used to generate the dataset and how to use and access of the dataset through the IRHUM database. Any interpretation of the isotope dataset is outside the scope of this publication.

  13. The IRHUM (Isotopic Reconstruction of Human Migration) database - bioavailable strontium isotope ratios for geochemical fingerprinting in France

    NASA Astrophysics Data System (ADS)

    Willmes, M.; McMorrow, L.; Kinsley, L.; Armstrong, R.; Aubert, M.; Eggins, S.; Falguères, C.; Maureille, B.; Moffat, I.; Grün, R.

    2014-03-01

    Strontium isotope ratios (87Sr / 86Sr) are a key geochemical tracer used in a wide range of fields including archaeology, ecology, food and forensic sciences. These applications are based on the principle that the Sr isotopic ratios of natural materials reflect the sources of strontium available during their formation. A major constraint for current studies is the lack of robust reference maps to evaluate the source of strontium isotope ratios measured in the samples. Here we provide a new data set of bioavailable Sr isotope ratios for the major geologic units of France, based on plant and soil samples (Pangaea data repository doi:10.1594/PANGAEA.819142). The IRHUM (Isotopic Reconstruction of Human Migration) database is a web platform to access, explore and map our data set. The database provides the spatial context and metadata for each sample, allowing the user to evaluate the suitability of the sample for their specific study. In addition, it allows users to upload and share their own data sets and data products, which will enhance collaboration across the different research fields. This article describes the sampling and analytical methods used to generate the data set and how to use and access the data set through the IRHUM database. Any interpretation of the isotope data set is outside the scope of this publication.

  14. Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry

    NASA Technical Reports Server (NTRS)

    Ricci, M. P.; Merritt, D. A.; Freeman, K. H.; Hayes, J. M.

    1994-01-01

    Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

  15. Improved isotope ratio measurement performance in liquid chromatography/isotope ratio mass spectrometry by removing excess oxygen.

    PubMed

    Hettmann, Elena; Brand, Willi A; Gleixner, Gerd

    2007-01-01

    A low dead volume oxygen scrubbing system was introduced in a commercially available liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) interface to enhance the analytical capability of the system. In the LC/IRMS interface carbon from organic samples is converted into CO(2) inside the mobile phase by wet chemical oxidation using peroxodisulfate (Na(2)S(2)O(8)). After passing the hot reaction zone, surplus oxygen (O(2)) remains dissolved in the liquid phase. Both CO(2) and O(2) diffuse through a transfer membrane into the helium carrier and are transferred to the mass spectrometer. The presence of O(2) in the ion source may have detrimental effects on measurement accuracy and precision as well as on filament lifetime. As a remedy, a new on-line O(2)-removing device has been incorporated into the system. The new O(2) scrubber consists of two parallel hot copper reduction reactors (0.8 mm i.d., active length 120 mm) and a switch-over valve between them. One reactor is regenerated using He/H(2) while the other is actively scavenging O(2) from the gas stream. The capacity of each reduction reactor, expressed as usage time, is between 40 and 50 min. This is sufficient for a single LC run for sugars and organic acids. A further increase of the reduction capacity is accompanied by a peak broadening of about 100%. After switching to a freshly reduced reactor the oxygen background and the delta(13)C values of the reference gas need up to 500 s to stabilize. For repeated injections the delta(13)C values of sucrose remain constant (+/-0.1 per thousand) for about 3000 s. The long-term stability for measurements of sucrose was 0.11 per thousand without the reduction oven and improved slightly to 0.08 per thousand with the reduction oven. The filament lifetime improved by more than 600%, thereby improving the long-term system stability and analytical efficiency. In addition the costs per analysis were reduced considerably. PMID:18041012

  16. USE OF STABLE CARBON ISOTOPE RATIOS OF FATTY ACIDS TO EVALUATE MICROBIAL CARBON SOURCES IN TERRESTRIAL ENVIRONMENTS

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

  17. USE OF THE COMPOSITION AND STABLE CARBON ISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (Gamma 13C) of individual microbial phospholipid fatty acids (PLFAS) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SO...

  18. Early Eocene SST recorded in clumped isotopic ratios of fish otoliths of North Sea Basin, Belgium

    NASA Astrophysics Data System (ADS)

    Kannan, P.; Vanhove, D.; Ghosh, P.

    2012-12-01

    Application of clumped isotope thermometry (Ghosh et al., 2007) in well preserved fish otoliths reveals environmental temperature. Fossil specimen of otoliths from marginal marine sedimentary sequence belonging to Ypresian (ca. 50.9 Ma) age reveals environmental temperature and salinity at the time of deposition. Fossil otoliths from two demersal, non-migratory species belonging to genuses namely Neobythitinorum subregularis and Paraconger papoiniti are considered here for this study. Intertaxon clumped isotope ratios allows to distinguish between the temperature habitat of fishes considered. Sedimentary record from the study area suggests large sea level changes and deposition close to shore line (Steurbaut, 2006). It was estimated that 150 kys was the time taken for deposition of the sequence from which the otolith fossils were retrieved (Steurbaut, 2006). The clumped isotope ratio and temperature estimates based on the otoliths composition are classified into two categories. Firstly, genus Neobythitinorum subregularis registering both low temperature (2 and 5°C) and high temperature (30 and 36°C) observed in eight specimens analysed. Secondly, genus Paraconger papoiniti registers warm water condition with consistent temperature of 32±2° C observed in six specimens analysed in this study. Based on the temperature estimates we conclude that North Sea water temperature was 20°C warmer compared to present day record of long time average during early Eocene. This estimate is consistent with previous estimates (Vanhove et al., 2011) based on stable isotope composition. Several hypotheses proposed previously will be explained and the inter-taxonomic variability will be explored in this presentation.

  19. In-Vivo Zinc Metabolism by Isotope Ratio Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this chapter is to highlight some of the methodological and technical issues surrounding the in vivo use of stable isotopes and to provide examples of how such studies have advanced our knowledge of human zinc metabolism. The advantages and disadvantages of the currently available in...

  20. Strontium isotope ratios and the origin of anorthosites

    SciTech Connect

    Vinogradov, V.I.

    1986-01-01

    Anorthosites are rocks consisting almost completely of calcic plagioclase, usually from andesine to labradorite. They are not widespread, and until recently were of no economic interest. However, with the advance of the new global tectonics, which has excited considerable interest in the structure and composition of upper-mantle rocks, interest in the anorthosites has grown. This has particularly been the case since the discovery of anorthosites on the moon, where they appear to be more widespread than on the earth. Data have recently been obtained on the strontium isotope compositions of anorthosite intrusions in the Dzhugdzhur-Stanovoy zone and in the rocks surrounding them, which have revealed some unexpected features. The paper describes the geological features of anorthosites, initial concepts on strontium isotope geochemistry, strontium isotope compositions of this region, and discusses some genetic consequences from the isotope data. Although the data of this study are insufficient to determine the origin of anorthosites, the data indicate several points which should be considered in following studies. 11 references, 1 figure.

  1. Uranium and Calcium Isotope Ratio Measurements using the Modified Total Evaporation Method in TIMS

    NASA Astrophysics Data System (ADS)

    Richter, S.; Kuehn, H.; Berglund, M.; Hennessy, C.

    2010-12-01

    A new version of the "modified total evaporation" (MTE) method for isotopic analysis by multi-collector thermal ionization mass spectrometry (TIMS), with high analytical performance and designed in a more user-friendly and routinely applicable way, is described in detail. It is mainly being used for nuclear safeguards measurements of U and Pu and nuclear metrology, but can readily be applied to other scientific tasks in geochemistry, e.g. for Sr, Nd and Ca, as well. The development of the MTE method was organized in collaboration of several "key nuclear mass spectrometry laboratories", namely the New Brunswick Laboratory (NBL), the Institute for Transuranium Elements (ITU), the Safeguards Analytical Laboratory (now Safeguards Analytical Services, SGAS) of the International Atomic Energy Agency (IAEA) and the Institute for Reference Materials and Measurements (IRMM), with IRMM taking the leading role. The manufacturer of the TRITON TIMS instrument, Thermo Fisher Scientific, integrated this method into the software of the instrument. The development has now reached its goal to become a user-friendly and routinely useable method for uranium isotope ratio measurements with high precision and accuracy. Due to the use of the “total evaporation” (TE) method the measurement of the "major" uranium isotope ratio 235U/238U is routinely being performed with a precision of 0.01% to 0.02%. The use of a (certified) reference material measured under comparable conditions is emphasized to achieve an accuracy at a level of 0.02% - depending on the stated uncertainty of the certified value of the reference material. In contrast to the total evaporation method (TE), in the MTE method the total evaporation sequence is interrupted on a regular basis to allow for correction for background from peak tailing, internal calibration of a secondary electron multiplier (SEM) detector versus the Faraday cups, and ion source re-focusing. Therefore, the most significant improvement using the

  2. Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Koppmann, R.; Krebsbach, M.; Hofzumahaus, A.; Rohrer, F.

    2013-11-01

    During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer (PBL) and the lower free troposphere (LFT) over south-west Germany using the ZEppelin Based Isotope Sampler (ZEBIS). These samples were analysed with respect to volatile organic compound (VOC) mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer (GC-C-IRMS). In this study we present results for toluene, one of the major anthropogenic pollutants, which emphasise the viability of isotope ratio measurements in VOC for atmospheric research, especially to study VOC sources or to track both dynamical and chemical processes. In situ measurements of CO mixing ratios on board the Zeppelin NT were used to allocate the air samples either to the PBL or the LFT. In the PBL we observed rather fresh emissions mixing into the background air. We estimated a toluene source isotope ratio of δ13C = -28.2 ± 0.5‰. Samples from the PBL and the LFT were clearly distinguishable by means of their mixing ratio and isotope ratio signatures. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We calculated the photochemical age of toluene in the atmosphere in two different ways using isotope ratios and mixing ratios. The results differ strongly in the PBL, probably due to mixing processes, but are compatible with each other in the LFT. Here, they correlate with a slope of 0.90±0.31.

  3. Stable carbon isotope ratios of rock varnish organic matter: a new paleoenvironmental indicator.

    PubMed

    Dorn, R I; Deniro, M J

    1985-03-22

    Stable carbon isotope ratios of organic matter in rock varnishes of Holocene age from western North America and the Middle East show a strong association with the environment. This isotopic variability reflects the abundance of plants with different photosynthetic pathways in adjacent vegetation. Analyses of different layers of varnish on late Pleistocene desert landforms indicate that the carbon isotopic composition of varnish organic matter is a paleoenvironmental indicator. PMID:17777781

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

    PubMed

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

    2014-01-01

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms. PMID:24853618

  5. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    SciTech Connect

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  6. Multi-collector Isotope Ratio Mass Spectrometer -- Operational Performance Report

    SciTech Connect

    Appelhans, Anthony D; Olson, John E; Watrous, Matthew G; Ward, Michael B.; Dahl, David A.

    2010-12-01

    This report describes the operational testing of a new magnetic sector mass spectrometer that utilizes seven full-sized discrete dynode electron multipliers operating simultaneously. The instrument includes a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated sufficiently to allow a full-sized discrete dynode pulse counting multiplier to be used to measure each isotope beam. The performance of the instrument was measured using SRM 996 (244Pu spike) at loadings of 2.4 and 12 fg on resin beads and with SRM 4350B Columbia River Sediment samples. The measured limit of detection (3s) for 240Pu was 3.4 attograms for SRM 996. The limit of quantitation (LOQ), defined as 10 s, was 11.2 attograms. The measured concentration of 239Pu in the CRS standard was 152 ± 6 fg/g.

  7. High Spatial Resolution Isotope Ratio Imaging and 3D Reconstruction of Presolar SiC Grains

    NASA Astrophysics Data System (ADS)

    Lyon, I. C.; Henkel, T.; Clarke, A.

    2015-07-01

    Presolar SiC grains have been analysed with a new NanoSIMS for isotope ratio measurements of C, N and Si. High spatial resolution imaging suggests that nitrogen isotope heterogeneity within the grains may lead to anomalous results in the literature.

  8. Influence of isotopic re-equilibration on speleothem and fluid inclusion isotope ratios after primary calcite precipitation

    NASA Astrophysics Data System (ADS)

    Kluge, Tobias; Haderlein, Astrid; Weißbach, Therese

    2016-04-01

    Oxygen isotope ratios in speleothems (notably stalagmites) have been used since decades to successfully infer paleotemperatures and deduce paleo-environmental information. In addition, recent technical developments allow to increasingly use fluid inclusions as an archive for drip-water and together with the surrounding calcite as paleothermometer. A basic requirement for isotope data interpretation is the complete knowledge of the fractionation between calcite and fluid. Most laboratory and in-situ cave experiments focus on calcite growth and the isotope fractionation between calcite and feed solution. Potential isotope exchange and re-equilibration processes after the initial deposition have mostly been neglected. However, experiments of Oelkers et al. (2015) showed that the isotope exchange between minerals and fluid can proceed rapidly (within days), even at chemical equilibrium. In hydrous Mg carbonates a similar process of continuous isotope exchange between carbonate and fluid was observed after the carbonate precipitation was completed (Mavromatis et al., 2015). These observations suggest that the isotope ratios of speleothem calcite may be affected by this continuous exchange, likely driving the isotope composition continuously towards equilibrium at the respective cave conditions. In addition, fluid inclusions are suspected to be sensitive to an isotope exchange with the surrounding carbonate highlighting the need to precisely understand and quantify this effect. We assessed the oxygen isotope exchange between calcite and solution at chemical equilibrium conditions with theoretical estimates and laboratory experiments over an intermediate time scale (hours-weeks). A large isotope gradient (~20 ‰)) between solution and calcite was prepared in the experiment to investigate the dynamics of this re-equilibration process. We used a theoretical model based on a Rayleigh fractionation approach and the direct comparison with the experiment to determine

  9. Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Koppmann, R.; Krebsbach, M.

    2013-04-01

    Measurements of stable carbon isotope ratios in VOC are a powerful tool to identify sources or to track both dynamical and chemical processes. During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer and the lower free troposphere over south-west Germany. These samples were analysed with respect to VOC mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer. In this study we present the results for toluene, one of the major anthropogenic pollutants. In the boundary layer we observed rather fresh emissions mixing into the background and derived a toluene source isotope ratio of δ13C = -28.2 ± 0.5 ‰. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We estimated the photochemical age of toluene in the atmosphere in two different ways (using isotope ratios and mixing ratios, respectively). The results differ strongly in the planetary boundary layer, probably due to mixing processes, but are compatible with each other in the free troposphere.

  10. Temporal trends in nitrogen isotope ratios of winter flounder collected from Rhode Island coastal systems

    EPA Science Inventory

    Nitrogen isotope ratios (15N) were measured in muscle tissue of juvenile winter flounder, Pseudopleuronectes americanus, collected from several estuarine systems along the coast of Rhode Island, USA, including Narragansett Bay, Narrow River and three coastal lagoons. Fish collect...

  11. Accuracy of delta 18O isotope ratio measurements on the same sample by continuous-flow isotope-ratio mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The doubly labeled water method is considered the reference method to measure energy expenditure. Conventional mass spectrometry requires a separate aliquot of the same sample to be prepared and analyzed separately. With continuous-flow isotope-ratio mass spectrometry, the same sample could be analy...

  12. Quantum statistical thermodynamics of hot finite nuclear systems: Temperatures and isotopic yield ratios

    SciTech Connect

    Majka, Z.; Staszel, P.; Cibor, J.; Natowitz, J.B.; Hagel, K.; Li, J.; Mdeiwayeh, N.; Wada, R.; Zhao, Y.

    1997-06-01

    We investigate the importance of the quantum statistics and deexcitation of primary fragments on the isotope yield ratio temperature determination. A phenomenological formula is presented which allows derivation of the temperature of the decaying nuclear system at the freeze-out time from the measured double yield ratios of two isotope pairs. This prescription is applied to the recent ALADIN and EOS Collaboration data. {copyright} {ital 1997} {ital The American Physical Society}

  13. Isotope ratios of uranium using high resolution inductively coupled plasma-mass spectrometry (ICP-MS)

    SciTech Connect

    Hearn, R.; Wildner, H.

    1998-12-31

    Actinide element isotope ratios have been determined in environmental samples using high resolution ICP-MS with ultrasonic nebulization. Precisions as low as 0.1% RSD have been achieved using various methods of acquisition. The methodology has been used for environmental monitoring of uranium isotope ratios as an indicator of nuclear activity. Also, it has been applied to calcite dating studies as a measure of past geochemical disturbances.

  14. Graphite Isotope Ratio Method Development Report: Irradiation Test Demonstration of Uranium as a Low Fluence Indicator

    SciTech Connect

    Reid, B.D.; Gerlach, D.C.; Love, E.F.; McNeece, J.P.; Livingston, J.V.; Greenwood, L.R.; Petersen, S.L.; Morgan, W.C.

    1999-10-20

    This report describes an irradiation test designed to investigate the suitability of uranium as a graphite isotope ratio method (GIRM) low fluence indicator. GIRM is a demonstrated concept that gives a graphite-moderated reactor's lifetime production based on measuring changes in the isotopic ratio of elements known to exist in trace quantities within reactor-grade graphite. Appendix I of this report provides a tutorial on the GIRM concept.

  15. Observations and sources of carbon and nitrogen isotope ratio variation of pentaerythritol tetranitrate (PETN).

    PubMed

    Howa, John D; Lott, Michael J; Ehleringer, James R

    2014-11-01

    Isotope ratio analysis allows forensic investigators to discriminate materials that are chemically identical but differ in their isotope ratios. Here we focused on the discrimination of pentaerythritol tetranitrate (PETN), an explosive with military and civilian applications, using carbon (δ(13)C) and nitrogen (δ(15)N) isotope ratios. Our goal was to understand some of the factors influencing the isotope ratios of commercially manufactured PETN. PETN was isolated from bulk explosives using preparative HPLC, which reduced chemical and isotopic within-sample variability. We observed isotope ratio variation in a survey of 175 PETN samples from 22 manufacturing facilities, with δ(13)C values ranging from -49.7‰ to -28.0‰ and δ(15)N values ranging from -48.6‰ to +6.2‰. Both within-sample variability and variation of PETN within an explosive block were much smaller than between-sample variations. Isotopic ratios of PETN were shown to discriminate explosive blocks from the same manufacturer, whereas explosive component composition measurements by HPLC were not able to do so. Using samples collected from three industrial PETN manufacturers, we investigated the isotopic relationship between PETN and its reactants, pentaerythritol (PE) and nitric acid. Our observations showed that δ(13)C values of PETN were indistinguishable from that of the reactant pentaerythritol. Isotopic separation between nitric acid and PETN was consistent within each sampled manufacturer but differed among manufacturers, and was likely dependent upon reaction conditions. These data indicate that δ(13)C variation in PETN is dependent on δ(13)C variation of PE supplies, while δ(15)N variation in PETN is due to both nitric acid δ(15)N and reaction conditions. PMID:25244291

  16. Mare basalt genesis - Modeling trace elements and isotopic ratios

    NASA Astrophysics Data System (ADS)

    Binder, A. B.

    1985-11-01

    Various types of mare basalt data have been synthesized, leading to the production of an internally consistent model of the mare basalt source region and mare basalt genesis. The model accounts for the mineralogical, major oxide, compatible siderophile trace element, incompatible trace element, and isotopic characteristics of most of the mare basalt units and of all the pyroclastic glass units for which reliable data are available. Initial tests of the model show that it also reproduces the mineralogy and incompatible trace element characteristics of the complementary highland anorthosite suite of rocks and, in a general way, those of the lunar granite suite of rocks.

  17. High-precision measurement of chlorine stable isotope ratios

    USGS Publications Warehouse

    Long, A.; Eastoe, C.J.; Kaufmann, R.S.; Martin, J.G.; Wirt, L.; Finley, J.B.

    1993-01-01

    We present an analysis procedure that allows stable isotopes of chlorine to be analyzed with precision sufficient for geological and hydrological studies. The total analytical precision is ?????0.09%., and the present known range of chloride in the surface and near-surface environment is 3.5???. As Cl- is essentially nonreactive in natural aquatic environments, it is a conservative tracer and its ??37Cl is also conservative. Thus, the ??37Cl parameter is valuable for quantitative evaluation of mixing of different sources of chloride in brines and aquifers. ?? 1993.

  18. A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

    USGS Publications Warehouse

    Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

    2015-01-01

    This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

  19. 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.

  20. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kreuzer, Helen W.; Horita, Juske; Moran, James J.; Tomkins, Bruce; Janszen, Derek B.; Carman, April J.

    2012-01-03

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  1. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kruzer, Helen W; Horita, Juske; Moran, James J; Tomkins, Bruce A; Janszen, Derek B; Carman, April

    2012-01-01

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  2. Atmospheric helium isotope ratio: Possible temporal and spatial variations

    NASA Astrophysics Data System (ADS)

    Sano, Yuji; Furukawa, Yukiko; Takahata, Naoto

    2010-09-01

    The atmospheric 3He/ 4He ratio has been considered to be constant on a global scale, because the residence time of helium is significantly longer than the mixing time in the atmosphere. However, this ratio may be decreasing with time owing to the anthropogenic release of crustal helium from oil and natural gas wells, although this observation has been disputed. Here, we present the 3He/ 4He ratios of old air trapped in historical slags in Japan and of modern surface air samples collected at various sites around the world, measured with a newly developed analytical system. In air helium extracted from metallurgical slag found at refineries in operation between AD 1603 and 1907 in Japan, we determined a mean 3He/ 4He ratio of (5106 ± 108) × 10 -5 R HESJ (where R HESJ is the 3He/ 4He ratio of the Helium Standard of Japan), which is consistent with the previously reported value of (5077 ± 59) × 10 -5 R HESJ for historical slags in France and United Arab Emirates and about 4% higher than that of average modern air, (4901 ± 4) × 10 -5 R HESJ. This result implies that the air 3He/ 4He ratio has decreased with time as expected by anthropogenic causes. Our modern surface air samples revealed that the 3He/ 4He ratio increases from north to south at a rate of (0.16 ± 0.08) × 10 -5 R HESJ/degree of latitude, suggesting that the low 3He/ 4He ratio originates in high-latitude regions of the northern hemisphere, which is consistent with the fact that most fossil fuel is extracted and consumed in the northern hemisphere.

  3. Do Strontium Isotope Ratios of Animal Bone and Teeth Really Reflect the Isotope Ratios of its birth- and growth-places?

    NASA Astrophysics Data System (ADS)

    Minami, M.; Goto, A.; Suzuki, K.; Kato, T.; Watanabe, K.; Hasegawa, T.

    2007-12-01

    Strontium enters the human body through the food chain as nutrients pass from bedrock through soil and water to plants and animals. Strontium substitutes for calcium in the hydroxyapatite mineral of skeletal tissue, and is stored there. 87Sr/86Sr ratios in an individual's bone and teeth could directly reflect the isotopic ratios found in the plants and animals that she or he consumed, which reflect the isotope ratios found in the soil and bedrock of that geologic region. Therefore, 87Sr/86Sr ratios of human skeletons could be useful tools for assessing human residential mobility in prehistory, and many studies on them have been often made. In this study, to evaluate whether the 87Sr/86Sr ratio of a bone or teeth really reflects the isotopic ratios of its birth and growth places, several bone and teeth samples were measured for 87Sr/86Sr ratios, compared with 87Sr/86Sr ratios of geological samples in their growth-places. Bone and teeth samples were leached with 5% acetic acid. After drying, samples were ashed in a muffle furnace at 825°C for 8h, and then digested in nitric acid, followed by cation exchange chromatography with 2.4M hydrochloric acid. 87Sr/86Sr ratios were measured using a thermal ionization mass Spectrometer (VG Sector 54) or an inductively coupled plasma mass spectrometer (Finnigan ELEMENT2). A modern boar bone collected at Asuke, Toyota City, Aichi prefecture, Japan showed a 87Sr/86Sr of 0.71001±0.00002 (2 σ), while stream sediments in the Asuke area showed around 0.710 (Asahara et al., 2006). The 87Sr/86Sr ratio of a modern black bass bone collected from Lake Biwa, Shiga prefecture, Japan was 0.71215±0.00002, while those of surface water in Lake Biwa was 0.71233±0.00002. The similar 87Sr/86Sr ratios between bone and its provenance geology could indicate that the 87Sr/86Sr ratios of bones reflect the isotopic ratios of the birth- and growth-places. The more results of modern and fossil skeletons will be shown in our presentation.

  4. Method for the determination of concentration and stable carbon isotope ratios of atmospheric phenols

    NASA Astrophysics Data System (ADS)

    Saccon, M.; Busca, R.; Facca, C.; Huang, L.; Irei, S.; Kornilova, A.; Lane, D.; Rudolph, J.

    2013-05-01

    A method for the determination of the stable carbon isotopic composition of atmospheric nitrophenols in the gas and particulate phases is presented. It has been proposed to use the combination of concentration and isotope ratio measurements of precursor and product to test the applicability of results of laboratory studies to the atmosphere. Nitrophenols are suspected to be secondary products formed specifically from the photooxidation of volatile organic compounds. XAD-4™ resin was used as an adsorbent on quartz filters to sample ambient phenols using conventional high-volume air samplers at York University in Toronto, Canada. Filters were extracted in acetonitrile, with a HPLC clean-up step and a solid phase extraction step prior to derivatization with BSTFA. Concentration measurements were done with gas chromatography-mass spectrometry and gas chromatography-isotope ratio mass spectrometry was used for isotope ratio analysis. The technique presented allows for atmospheric compound-specific isotopic composition measurements for five semi-volatile phenols with an estimated accuracy of 0.3‰ to 0.5‰ at atmospheric concentrations exceeding 0.1 ng m-3 while the detection limits for concentration measurements are in the pg m-3 range. Isotopic fractionation throughout the entire extraction procedure and analysis was proven to be below the precision of the isotope ratio measurements. The method was tested by conducting ambient measurements from September to December 2011.

  5. Method for the determination of concentration and stable carbon isotope ratios of atmospheric phenols

    NASA Astrophysics Data System (ADS)

    Saccon, M.; Busca, R.; Facca, C.; Huang, L.; Irei, S.; Kornilova, A.; Lane, D.; Rudolph, J.

    2013-11-01

    A method for the determination of the stable carbon isotopic composition of atmospheric nitrophenols in the gas and particulate phases is presented. It has been proposed to use the combination of concentration and isotope ratio measurements of precursor and product to test the applicability of results of laboratory studies to the atmosphere. Nitrophenols are suspected to be secondary products formed specifically from the photooxidation of volatile organic compounds. XAD-4TM resin was used as an adsorbent on quartz filters to sample ambient phenols using conventional high volume air samplers at York University in Toronto, Canada. Filters were extracted in acetonitrile, with a HPLC (high-performance liquid chromatography) clean-up step and a solid phase extraction step prior to derivatization with BSTFA (bis(trimethylsilyl) trifluoroacetamide). Concentration measurements were done with gas chromatography-mass spectrometry and gas chromatography-isotope ratio mass spectrometry was used for isotope ratio analysis. The technique presented allows for atmospheric compound-specific isotopic composition measurements for five semi-volatile phenols with an estimated accuracy of 0.3-0.5‰ at atmospheric concentrations exceeding 0.1 ng m-3 while the detection limits for concentration measurements are in the pg m-3 range. Isotopic fractionation throughout the entire extraction procedure and analysis was proven to be below the precision of the isotope ratio measurements. The method was tested by conducting ambient measurements from September to December 2011.

  6. Bayesian Integration of Isotope Ratios for Geographic Sourcing of Castor Beans

    SciTech Connect

    Webb-Robertson, Bobbie-Jo M.; Kreuzer, Helen W.; Hart, Garret L.; Ehleringer, James; West, Jason B.; Gill, Gary A.; Duckworth, Douglas C.

    2012-08-15

    Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H) and strontium (Sr) isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 6 0 . 9 {+-} 2 . 1 % versus 5 5 . 9 {+-} 2 . 1 % and 4 0 . 2 {+-} 1 . 8 % for the light element and strontium (Sr) isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model.

  7. Are sulfur isotope ratios sufficient to determine the antiquity of sulfate reduction. [implications for chemical evolution

    NASA Technical Reports Server (NTRS)

    Ashendorf, D.

    1980-01-01

    Possible limitations on the use of sulfur isotope ratios in sedimentary sulfides to infer the evolution of microbial sulfate reduction are discussed. Current knowledge of the ways in which stable sulfur isotope ratios are altered by chemical and biological processes is examined, with attention given to the marine sulfur cycle involving various microbial populations, and sulfur reduction processes, and it is noted that satisfactory explanations of sulfur isotope ratios observed in live organisms and in sediments are not yet available. It is furthermore pointed out that all members of the same genus of sulfate reducing bacteria do not always fractionate sulfur to the same extent, that the extent of sulfur fractionation by many sulfate-reducing organisms has not yet been determined, and that inorganic processes can also affect sulfur isotope fractionation values. The information currently available is thus concluded to be insufficient to determine the time of initial appearance of biological sulfate reduction.

  8. Isotope ratio and trace element imaging of pyrite grains in gold ores

    NASA Astrophysics Data System (ADS)

    Fleming, Ronald H.; Bekken, Barbara M.

    1995-05-01

    Secondary ion mass spectrometry techniques for imaging measurements of 34S/32S isotope ratios and quantitative trace element concentrations in pyrite mineral grains have been demonstrated. Test samples show that the 34S/32S isotope ratios are constant within Poisson error, independent of image position. Variable 34S/32S isotope ratios have been found within a a single pyrite grain in a sample of gold ore from the Carlin mine in the Carlin District of Nevada. The locations of trace gold concentrations in this ore sample correlate with relative 34S enrichment. Imaging has the inherent problem of spreading already limited minor isotope signals among many pixels. This problem can be overcome with improved analysis methodology including new electron multiplier circuitry to accommodate more intense secondary ion signals, stable data collection over relatively long time periods, and improved software. High mass resolution imaging and careful neutralization of ion beam induced sample charging are also required.

  9. Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Qi, H.P.; Coplen, T.B.

    2003-01-01

    Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

  10. Seven Channel Multi-collector Isotope Ratio Mass Spectrometer

    SciTech Connect

    Anthony D. Appelhans

    2008-07-01

    A new magnetic sector mass spectrometer that utilizes seven full-sized discrete dynode electron multipliers operating simultaneously has been designed, constructed and is in preliminary testing. The instrument utilizes a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated sufficiently (35 mm) to allow a full-sized discrete dynode pulse counting multiplier to be used for each beam. The ion dispersion lens is a two element electrostatic 90 degree sector device that causes the beam-to-beam dispersion to increase faster than the intra-beam dispersion. Each multiplier is contained in an isolated case with a deflector/condenser lens at the entrance. A 9-sample filament cartridge is mounted on a micro-manipulator two-axis stage that enables adjustment of the filament position with 10 micron resolution within the ion lens. Results of initial testing with actinides will be presented.

  11. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  12. Intracellular metabolite levels shape sulfur isotope fractionation during microbial sulfate respiration

    PubMed Central

    Wing, Boswell A.; Halevy, Itay

    2014-01-01

    We present a quantitative model for sulfur isotope fractionation accompanying bacterial and archaeal dissimilatory sulfate respiration. By incorporating independently available biochemical data, the model can reproduce a large number of recent experimental fractionation measurements with only three free parameters: (i) the sulfur isotope selectivity of sulfate uptake into the cytoplasm, (ii) the ratio of reduced to oxidized electron carriers supporting the respiration pathway, and (iii) the ratio of in vitro to in vivo levels of respiratory enzyme activity. Fractionation is influenced by all steps in the dissimilatory pathway, which means that environmental sulfate and sulfide levels control sulfur isotope fractionation through the proximate influence of intracellular metabolites. Although sulfur isotope fractionation is a phenotypic trait that appears to be strain specific, we show that it converges on near-thermodynamic behavior, even at micromolar sulfate levels, as long as intracellular sulfate reduction rates are low enough (<<1 fmol H2S⋅cell−1⋅d−1). PMID:25362045

  13. Certification of the Uranium Isotopic Ratios in Nbl Crm 112-A, Uranium Assay Standard (Invited)

    NASA Astrophysics Data System (ADS)

    Mathew, K. J.; Mason, P.; Narayanan, U.

    2010-12-01

    Isotopic reference materials are needed to validate measurement procedures and to calibrate multi-collector ion counting detector systems. New Brunswick Laboratory (NBL) provides a suite of certified isotopic and assay standards for the US and international nuclear safeguards community. NBL Certified Reference Material (CRM) 112-A Uranium Metal Assay Standard with a consensus value of 137.88 for the 238U/235U ratio [National Bureau of Standards -- NBS, currently named National Institute for Standards and Technology, Standard Reference Material (SRM) 960 had been renamed CRM 112-A] is commonly used as a natural uranium isotopic reference material within the earth science community. We have completed the analytical work for characterizing the isotopic composition of NBL CRM 112-A Uranium Assay Standard and NBL CRM 145 (uranyl nitrate solution prepared from CRM 112-A). The 235U/238U isotopic ratios were characterized using the total evaporation (TE) and the modified total evaporation (MTE) methods. The 234U/238U isotope ratios were characterized using a conventional analysis technique and verified using the ratios measured in the MTE analytical technique. The analysis plan for the characterization work was developed such that isotopic ratios that are traceable to NBL CRM U030-A are obtained. NBL is preparing a certificate of Analysis and will issue a certificate for Uranium Assay and Isotopics. The results of the CRM 112-A certification measurements will be discussed. These results will be compared with the average values from Richter et al (2010). A comparison of the precision and accuracy of the measurement methods (TE, MTE and Conventional) employed in the certification will be presented. The uncertainties in the 235U/238U and 234U/238U ratios, calculated according to the Guide to the Expression of Uncertainty in Measurements (GUM) and the dominant contributors to the combined standard uncertainty will be discussed.

  14. STABLE ISOTOPE RATIOS IN ARCHIVED STRIPED BASS SCALES

    EPA Science Inventory

    In recent years fishermen and scientists have noted that striped bass caught along the East Coast of the United States have reduced weight to length ratios with many of the fish caught in Chesapeake Bay exhibiting skin lesions. Several theories have been suggested to explain thes...

  15. Stable isotopic studies on chitin. III. The D/H and 18O/ 16O ratios in arthropod chitin

    NASA Astrophysics Data System (ADS)

    Schimmelmann, Arndt; DeNiro, Michael J.

    1986-07-01

    Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ 18O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ 18O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ 18O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ 18O values will require specific information about the habits and habitats of the species involved in the analysis.

  16. Lead isotope ratios in tree bark pockets: an indicator of past air pollution in the Czech Republic.

    PubMed

    Conkova, M; Kubiznakova, J

    2008-10-15

    Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 microg g(-1)) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 microg g(-1)) was found at the Kosetice EMEP "background pollution" site. Changes in (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the (206)Pb/(207)Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the (208)Pb/(206)Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ((206)Pb/(207)Pb of 1.11) lead to lower (206)Pb/(207)Pb in bark pockets over time. High-radiogenic lignite-derived Pb ((206)Pb/(207)Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic. PMID:18597820

  17. Source characteristics of marine oils as indicated by carbon isotopic ratios of volatile hydrocarbons

    SciTech Connect

    Chung, H.M.; Claypool, G.E.; Rooney, M.A. ); Squires, R.M. )

    1994-03-01

    Carbon isotopic ratios of volatile hydrocarbon fractions of marine oils are diagnostic of organic facies and depositional environments of source rocks. For carbonate oils, low-molecular-weight volatile hydrocarbons (< C[sub 9]) are isotopically lighter than high-molecular-weight volatile hydrocarbons (C[sub 9]-C[sub 17]). In contrast, for deltaic oils, low-molecular-weight volatile hydrocarbons are isotopically heavier than high-molecular-weight volatile hydrocarbons. Marine shale oils show patterns intermediate between carbonate and deltaic oils. This relative variation of carbon isotopic ratios among volatile hydrocarbons of oils is explained by earlier expulsion of marine oils derived from isotopically homogeneous (algal-bacterial) kerogens in rich source rocks, and secondary cracking of petroleum prior to expulsion for marine oils derived from isotopically heterogeneous (terrestrial) kerogens in lean source rocks. In basins with multiple source rocks, carbon isotopic ratios of volatile hydrocarbons are useful for determining oil-oil correlation and for inferring oil-source rock relationship. 67 refs., 5 figs., 2 tabs.

  18. 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

  19. Final report of the key comparison CCQM-K98: Pb isotope amount ratios in bronze

    NASA Astrophysics Data System (ADS)

    Vogl, Jochen; Yim, Yong-Hyeon; Lee, Kyoung-Seok; Goenaga-Infante, Heidi; Malinowskiy, Dmitriy; Ren, Tongxiang; Wang, Jun; Vocke, Robert D., Jr.; Murphy, Karen; Nonose, Naoko; Rienitz, Olaf; Noordmann, Janine; Näykki, Teemu; Sara-Aho, Timo; Ari, Betül; Cankur, Oktay

    2014-01-01

    Isotope amount ratios are proving useful in an ever increasing array of applications that range from studies unravelling transport processes, to pinpointing the provenance of specific samples as well as trace element quantification by using isotope dilution mass spectrometry (IDMS). These expanding applications encompass fields as diverse as archaeology, food chemistry, forensic science, geochemistry, medicine and metrology. However, to be effective tools, the isotope ratio data must be reliable and traceable to enable the comparability of measurement results. The importance of traceability and comparability in isotope ratio analysis has already been recognized by the Inorganic Analysis Working Group (IAWG) within the CCQM. While the requirements for isotope ratio accuracy and precision in the case of IDMS are generally quite modest, 'absolute' Pb isotope ratio measurements for geochemical applications as well as forensic provenance studies require Pb isotope ratio measurements of the highest quality. To support present and future CMCs on isotope ratio determinations, a key comparison was urgently needed and therefore initiated at the IAWG meeting in Paris in April 2011. The analytical task within such a comparison was decided to be the measurement of Pb isotope amount ratios in water and bronze. Measuring Pb isotope amount ratios in an aqueous Pb solution tested the ability of analysts to correct for any instrumental effects on the measured ratios, while the measurement of Pb isotope amount ratios in a metal matrix sample provided a real world test of the whole chemical and instrumental procedure. A suitable bronze material with a Pb mass fraction between 10 and 100 mg•kg-1 and a high purity solution of Pb with a mass fraction of approximately 100 mg•kg-1 was available at the pilot laboratory (BAM), both offering a natural-like Pb isotopic composition. The mandatory measurands, the isotope amount ratios n(206Pb)/n(204Pb), n(207Pb)/n(204Pb) and n(208Pb)/n(204Pb

  20. Relation between hydrogen isotopic ratios of bone collagen and rain

    SciTech Connect

    Cormie, A.B.; Schwarcz, H.P. ); Gray, J. )

    1994-01-01

    The hydrogen isotopic value ([delta]D) of deer bone collagen is related to both [delta]D of rain during the growing season and growing season relative humidity (RH). With correction for the effects of RH, bone [delta]D is related to growing season rain [delta]D in a simple manner with a slope of 1.0. This indicates that, with RH correction, there are no additional sources of bias in the [delta]D of bone due to unaccounted for biologic or climatic effects. Due to a low sensitivity of bone [delta]D to RH effects, both yearly and growing season rain [delta]D can be estimated with considerable accuracy (R = 0.97 and R = 0.96) from bone collagen [delta]D and [delta][sup 15]N. Here, [delta][sup 15]N is used to correct bone [delta]D for the effects of RH. From these estimates of rain [delta]D, it may then be possible to evaluate temperature since the [delta]D of rain primarily reflects local temperature. Therefore, the measurement of bone collagen [delta]D has good potential for evaluating paleoclimates.

  1. Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

    PubMed

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2008-10-01

    Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment. PMID:18798196

  2. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    NASA Astrophysics Data System (ADS)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  3. Hydrogen isotope ratios of mouse tissues are influenced by a variety of factors other than diet

    SciTech Connect

    DeNiro, M.J.; Epstein, S.

    1981-12-16

    Hydrogen isotopes are fractionated during biochemical reactions in a variety of organisms. A number of experiments have shown that the D/H ratios of animals and their tissues are not controlled solely by the D/H ratios of their food. The authors performed a simple experiment which indicated that the D/H ratios of a significant fraction of the organically bonded hydrogen in animal tissues must be determined by the isotopic composition of water that the samples encounter. Aliquots of dried mouse brain and liver and mouse food were exposed to water vapors of different D/H ratios prior to isotopic analysis. The results of the experiment showed that at least 16 percent of the hydrogen in mouse brain is exchangeable with the hydrogen of water; the corresponding values for mouse liver and mouse food were 25 to 29 percent. (JMT)

  4. Analysis of the hydrogen and oxygen stable isotope ratios of beverage waters without prior water extraction using isotope ratio infrared spectroscopy.

    PubMed

    Chesson, Lesley A; Bowen, Gabriel J; Ehleringer, James R

    2010-11-15

    Hydrogen (δ(2)H) and oxygen (δ(18)O) stable isotope analysis is useful when tracing the origin of water in beverages, but traditional analytical techniques are limited to pure or extracted waters. We measured the isotopic composition of extracted beverage water using both isotope ratio infrared spectroscopy (IRIS; specifically, wavelength-scanned cavity ring-down spectroscopy) and isotope ratio mass spectrometry (IRMS). We also analyzed beer, sodas, juices, and milk 'as is' using IRIS. For IRIS analysis, four sequential injections of each sample were measured and data were corrected for sample-to-sample memory using injections (a) 1-4, (b) 2-4, and (c) 3-4. The variation between δ(2)H and δ(18)O values calculated using the three correction methods was larger for unextracted (i.e., complex) beverages than for waters. The memory correction was smallest when using injections 3-4. Beverage water δ(2)H and δ(18)O values generally fit the Global Meteoric Water Line, with the exception of water from fruit juices. The beverage water stable isotope ratios measured using IRIS agreed well with the IRMS data and fit 1:1 lines, with the exception of sodas and juices (δ(2)H values) and beers (δ(18)O values). The δ(2)H and δ(18)O values of waters extracted from beer, soda, juice, and milk were correlated with complex beverage δ(2)H and δ(18)O values (r = 0.998 and 0.997, respectively) and generally fit 1:1 lines. We conclude that it is possible to analyze complex beverages, without water extraction, using IRIS although caution is needed when analyzing beverages containing sugars, which can clog the syringe and increase memory, or alcohol, a known spectral interference. PMID:20941769

  5. Evaluating the status of uranium isotope ratio measurements using an inter-laboratory comparison campaign

    NASA Astrophysics Data System (ADS)

    Richter, S.; Alonso, A.; Truyens, J.; Kühn, H.; Verbruggen, A.; Wellum, R.

    2007-07-01

    The REIMEP 18 (Regular European Inter-laboratory Measurement Evaluation Programme) campaign for the measurement isotopic ratios of uranium in nitric acid solution was completed in December 2006. The task for all participating laboratories was to measure the uranium isotopic composition of four uranium samples ranging from depleted to slightly enriched uranium. With 71 participating laboratories REIMEP 18 has become the largest nuclear isotopic measurement campaign organized by IRMM so far. Participation in this kind of measurement campaign is an integral part of the external quality control required for nuclear safeguards laboratories worldwide. For the first time also a significant number of academic laboratories, mainly from the geochemistry area was included. Certification measurements were carried out at IRMM using state-of-the-art mass spectrometric methodology. A MAT511 UF6-gas source mass spectrometer (GSMS) was used to determine the n(235U)/n(238U) ratios and a TRITON thermal-ionization mass-spectrometer (TIMS) for the minor isotope ratios n(234U)/n(238U) and n(236U)/n(238U). Verification measurements on ampouled samples were performed successfully prior to sample shipping and showed good agreement with the certified ratios. The results of the REIMEP 18 campaign confirm in general the excellent capability of nuclear safeguards and scientific laboratories in measuring isotopic abundances of uranium, although some problems were discovered for the measurements of the minor isotope ratios n(234U)/n(238U) and n(236U)/n(238U) and the calculation of measurement uncertainties for isotope ratios in general. This paper describes the outcome of the REIMEP 18 campaign. It includes a graphical evaluation and discussion of the results, an evaluation of the applied measurement and calibration techniques and a discussion of conclusions and actions to be taken.

  6. A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

  7. Line shift, line asymmetry, and the ^6Li/^7Li isotopic ratio determination

    NASA Astrophysics Data System (ADS)

    Cayrel, R.; Steffen, M.; Chand, H.; Bonifacio, P.; Spite, M.; Spite, F.; Petitjean, P.; Ludwig, H.-G.; Caffau, E.

    2007-10-01

    Context: Line asymmetries are generated by convective Doppler shifts in stellar atmospheres, especially in metal-poor stars, where convective motions penetrate to higher atmospheric levels. Such asymmetries are usually neglected in abundance analyses. The determination of the ^6Li/^7Li isotopic ratio is prone to suffering from such asymmetries, as the contribution of ^6Li is a slight blending reinforcement of the red wing of each component of the corresponding ^7Li line, with respect to its blue wing. Aims: The present paper studies the halo star HD 74000 and estimates the impact of convection-related asymmetries on the Li isotopic ratio determination. Methods: Two methods are used to meet this aim. The first, which is purely empirical, consists in deriving a template profile from another element that can be assumed to originate in the same stellar atmospheric layers as Li I, producing absorption lines of approximately the same equivalent width as individual components of the ^7Li I resonance line. The second method consists in conducting the abundance analysis based on NLTE line formation in a 3D hydrodynamical model atmosphere, taking into account the effects of photospheric convection. Results: The results of the first method show that the convective asymmetry generates an excess absorption in the red wing of the ^7Li absorption feature that mimics the presence of ^6Li at a level comparable to the hitherto published values. This opens the possibility that only an upper limit on ^6Li/^7Li has thus far been derived. The second method confirms these findings. Conclusions: From this work, it appears that a systematic reappraisal of former determinations of ^6Li abundances in halo stars is warranted. Based on observations carried out at the European Southern Observatory (ESO), under prog. ID 75.D-0600. Tables 1-3, and additional references are only available in electronic form at http://www.aanda.org

  8. Forensic utility of isotope ratio analysis of the explosive urea nitrate and its precursors.

    PubMed

    Aranda, Roman; Stern, Libby A; Dietz, Marianne E; McCormick, Meghan C; Barrow, Jason A; Mothershead, Robert F

    2011-03-20

    Urea nitrate (UN) is an improvised explosive made from readily available materials. The carbon and nitrogen isotope composition of UN and its component ions, urea and nitrate, could aid in a forensic investigation. A method was developed to separate UN into its component ions for δ(15)N measurements by dissolving the sample with KOH, drying the sample, followed by removal of the urea by dissolution into 100% methanol. UN was synthesized to assess for preservation of the carbon and nitrogen isotope compositions of reactants (urea and nitric acid) and product UN. Based on nitrogen isotope mass balance, all UN samples contained varying amounts of excess nitric acid, making the ionic separation an essential step in the nitrogen isotope analysis. During UN synthesis experiments, isotopic composition of the reactants is preserved in the product UN, but the urea in the product UN is slightly enriched in (15)N (<1‰) relative to the reactant urea. Published isotopic compositions of UN reactants, urea and nitric acid, have large ranges (urea δ(15)N = -10.8 to +3.3‰; urea δ(13)C = -18.2 to -50.6‰; and nitric acid δ(15)N = -1.8 to +4.0‰). The preservation of isotopic composition of reactants in UN, along with a significant variability in isotopic composition of reactants, indicates that isotope ratio analysis may be used to test if urea or nitric acid collected during an investigation is a possible reactant for a specific UN sample. The carbon and nitrogen isotope ratios differ significantly between two field-collected UN samples, as well as the lab-synthesized UN samples. These observed variations suggest that this approach is useful for discriminating between materials which are otherwise chemically identical. PMID:20729019

  9. Helium Isotopic Ratios of Core Samples from IODP Exp. 319 (NanTroSEIZE Stage 2)

    NASA Astrophysics Data System (ADS)

    Horiguchi, K.; Matsuda, J.; Wiersberg, T.; Shimo, Y.; Tamura, H.; Kumagai, H.; Suzuki, K.; Saito, S.; Kinoshita, M.; Araki, E.; Byrne, T.; McNeill, L. C.; Saffer, D.; Takahashi, K.; Eguchi, N. O.; Toczko, S.

    2009-12-01

    IODP Exp.319 of Nankai Trough Seismogenic Zone Drilling Program Stage 2 started at May 2009. Various advanced technologies including first riser-based scientific ocean drilling were carried out at this cruise. The Hole C0009A (Site C0009/ Hole A) recovered cutting and partly core samples from 703.9-1604 mbsf by riser-drilling. The core samples were collected between the depth of 1510.5 and 1593.9 mbsf. Here we report preliminary helium isotopic ratios of these cores. We collected three types of samples for our study: (1) gas of cores, (2) whole round cores (100 cc) and (3) small whole round cores (10 cc). The gas samples were taken immediately after the core recovery. The gas samples were collected from each core section by using a syringe, and it was transferred to the glass bottle using the water displacement method. The glass bottle was made by Pyrex glass with vacuum valve at each end. We collected two sizes of whole round core samples (100 cc and 10 cc) The 100 cc cores were collected from the bottom and top sections of coring. The 10 cc cores were taken from the other sections. The outer parts of these samples were carefully removed to avoid contaminations from drilling fluid. After the removal of contamination, we immediately stored the 100 cc samples into vacuum container and 10 cc samples into plastic bag under a dry condition, respectively. The gas samples were measured for helium isotopic ratios. The noble gas measurement was carried out at Osaka University by using VG5400 mass spectrometer. We measured helium isotopic ratio and 4He/20Ne ratio. The latter is useful for making correction of the air contamination. The obtained result of helium isotopic ratios shows that the radiogenic helium is prominent in all samples. In addition, the helium isotope ratios show a trend that the ratio at shallower part is slightly higher than that at deeper part. It is conceivable that this trend is due to the larger radiogenic ingrowths at the deeper part. However, the

  10. A mechanistic model for interpretation of hydrogen and oxygen isotope ratios in tree-ring cellulose

    NASA Astrophysics Data System (ADS)

    Roden, John S.; Lin, Guanghui; Ehleringer, James R.

    2000-01-01

    A mechanistic model is presented to quantify both the physical and biochemical fractionation events associated with hydrogen and oxygen isotope ratios in tree-ring cellulose. The model predicts the isotope ratios of tree-rings, incorporating both humidity and source water environmental information. Components of the model include (1) hydrogen and oxygen isotope effects associated with leaf water enrichment; (2) incorporation of leaf water isotope ratio values into photosynthetic carbohydrates along with the biochemical fractionation associated with autotrophic synthesis; (3) transport of exported carbohydrates (such as sucrose) from leaves to developing xylem in shoots and stems where cellulose is formed; (4) a partial exchange of oxygen and hydrogen isotopes in carbohydrates with xylem sap water during conversion into cellulose; and (5) a biochemical fractionation associated with cellulose synthesis. A modified version of the Craig-Gordon model for evaporative enrichment adequately described leaf water δD and δ 18O values. The leaf water model was robust over a wide range of leaf waters for both controlled experiments and field studies, far exceeding the range of values to be expected under natural conditions. The isotopic composition of cellulose was modeled using heterotrophic and autotrophic fractionation factors from the literature as well as the experimentally derived proportions of H and O that undergo exchange with xylem water during cellulose synthesis in xylem cells of tree-rings. The fraction of H and O from carbohydrates that exchange with xylem sap water was estimated to be 0.36 and 0.42, respectively. The proportions were based on controlled, long-term greenhouse experiments and field studies where the variations in the δD and δ 18O of tree-ring cellulose were measured under different source water isotopic compositions. The model prediction that tree-ring cellulose contains information on environmental water source and atmospheric vapor pressure

  11. A 40-year record of Northern Hemisphere atmospheric carbon monoxide concentration and isotope ratios from the firn at Greenland Summit.

    NASA Astrophysics Data System (ADS)

    Place, P., Jr.; Petrenko, V. V.; Vimont, I.; Buizert, C.; Lang, P. M.; Edwards, J.; Harth, C. M.; Hmiel, B.; Mak, J. E.; Novelli, P. C.; Brook, E.; Weiss, R. F.; Vaughn, B. H.; White, J. W. C.

    2014-12-01

    Carbon Monoxide (CO) is an important atmospheric trace gas that affects the oxidative capacity of the atmosphere and contributes indirectly to climate forcing by being a major sink of tropospheric OH. A good understanding of the past atmospheric CO budget is therefore important for climate models attempting to characterize recent changes in the atmosphere. Previous work at NEEM, Greenland provided the first reconstructions of Arctic atmospheric history of CO concentration and stable isotope ratios (δC18O and δ13CO) from firn air, dating to the 1950s. In this new study, firn air was sampled from eighteen depth levels through the firn column at Summit, Greenland (in May 2013), yielding a second, independent record of Arctic CO concentration and isotopic ratios. Carbon monoxide stable isotope ratios were analyzed on replicate samples and using a newly developed system with improved precision allowing for a more robust reconstruction. The new CO concentration and stable isotope results overall confirm the earlier findings from NEEM, with a CO concentration peak around the 1970s and higher δC18O and δ13CO values associated with peak CO. Modeling and interpretation of the data are in progress.

  12. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, T.B.; Qi, H.

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

  13. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

  14. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry.

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2010-09-15

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ(2)H reproducibility (1σ standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN(2) is used as a moisture trap for gaseous hydrogen. PMID:20718408

  15. Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.; Date, A.R.

    1987-04-01

    The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

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

    PubMed

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

    2004-01-01

    The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications. PMID:15531795

  17. 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.

  18. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  19. Isotope ratio measurements of pg-size plutonium samples using TIMS in combination with "multiple ion counting" and filament carburization

    NASA Astrophysics Data System (ADS)

    Jakopic, Rozle; Richter, Stephan; Kühn, Heinz; Benedik, Ljudmila; Pihlar, Boris; Aregbe, Yetunde

    2009-01-01

    A sample preparation procedure for isotopic measurements using thermal ionization mass spectrometry (TIMS) was developed which employs the technique of carburization of rhenium filaments. Carburized filaments were prepared in a special vacuum chamber in which the filaments were exposed to benzene vapour as a carbon supply and carburized electrothermally. To find the optimal conditions for the carburization and isotopic measurements using TIMS, the influence of various parameters such as benzene pressure, carburization current and the exposure time were tested. As a result, carburization of the filaments improved the overall efficiency by one order of magnitude. Additionally, a new "multi-dynamic" measurement technique was developed for Pu isotope ratio measurements using a "multiple ion counting" (MIC) system. This technique was combined with filament carburization and applied to the NBL-137 isotopic standard and samples of the NUSIMEP 5 inter-laboratory comparison campaign, which included certified plutonium materials at the ppt-level. The multi-dynamic measurement technique for plutonium, in combination with filament carburization, has been shown to significantly improve the precision and accuracy for isotopic analysis of environmental samples with low-levels of plutonium.

  20. Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.; Pizzarello, S.; Cronin, J. R.; Yuen, G. U.

    1991-01-01

    A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

  1. Sulfur isotope ratios as evidence of dissolved sulfur uptake by salt marsh cordgrass. [Spartina alterniflora

    SciTech Connect

    Carlson, P.R. Jr.; Forrest, J.

    1985-06-01

    The difference in stable sulfur isotope ratios of sulfate and sulfide in marsh porewater was used to verify the uptake of hydrogen sulfide by the salt marsh cordgrass, Spartina alterniflora, in North Carlina salt marsh. Most of the plant sulfur derived from porewater sulfide was recovered as sulfate indicating that the sulfide had been oxidized within the plant. The analysis of sulfur isotope ratios of other marsh halophytes is suggested as a technique to determine whether sulfide is taken up by plants. 15 refs., 2 figs., 1 tab.

  2. Uptake of dissolved sulfide by Spartina alterniflora: evidence from natural sulfur isotope abundance ratios

    SciTech Connect

    Carlson, P.R. Jr.; Forrest, J.

    1982-05-07

    The difference in the stable sulfur isotope ratios of sulfate and sulfide in marsh pore water was used to verify the uptake of hydrogen sulfide by the salt marsh cordgrass Spartina alterniflora in a North Carolina salt marsh. Most of the plant sulfur derived from pore-water sulfide was recovered as sulfate, an indication that the sulfide had been oxidized within the plant. The anaysis of the sulfur isotope ratios of other coastal halophytes may be a useful technique for determining whether sulfide is taken up by plants in saline wetlands.

  3. 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).

  4. On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

    NASA Astrophysics Data System (ADS)

    Parkes, Stephen; Wang, Lixin; McCabe, Matthew

    2015-04-01

    In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a

  5. Correlation between multielement stable isotope ratio and geographical origin in Peretta cows' milk cheese.

    PubMed

    Manca, G; Franco, M A; Versini, G; Camin, F; Rossmann, A; Tola, A

    2006-03-01

    The aim of this study was to characterize the isotopic composition and protect "Peretta" cows' milk cheese, a typical product of Sardinia, against other cheeses of the same appearance sold under the same name, but made of raw materials from northern Europe. The study was concerned with 3 types of cheese: those produced in local dairies from milk from free-grazing or pasture-grazing cows in Sardinia (local dairy product), cheeses made on an industrial scale from milk produced by intensive farming in Sardinia (factory cheese), and cheeses made with raw materials imported from other countries (imported product). To distinguish the Sardinian cheeses from the imported product, the stable isotope ratios 13C/12C, 15N/14N, D/H, 34S/32S, and (18)O/(16)O were used. Determination of the isotopic data delta13C, delta15N, delta2H, and delta34S was performed in the casein fraction, whereas delta(18)O and delta13C were determined in the glycerol fraction. Measurements were performed by isotope ratio mass spectrometry. A comparison between mean values of the isotope ratios by statistical analysis (ANOVA and Tukey's test) showed that the greatest difference between the 3 types of cheese (local dairy, factory, and imported products) was in the 13C/12C, 34S/32S, and (18)O/(16)O isotope ratios. In the other parameters, either no differences (delta15N) or minimal differences (delta2H) were found. Evaluation of the data by multivariate statistical analysis (principal component analysis and hierarchical cluster analysis) revealed that the isotope characteristics of the factory products were similar to those of the cheeses produced from imported raw materials, whereas a difference was found between the local dairy-produced cheeses and the products in the other 2 categories. PMID:16507675

  6. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption

    NASA Astrophysics Data System (ADS)

    Kawashima, Hiroto; Murakami, Mai

    2014-06-01

    The isotopic analysis of atmospheric volatile organic compounds (VOCs), and in particular of their stable carbon isotope ratio (δ13C), could potentially be used as an effective tool for identifying the sources of VOCs. However, to date, there have been very few such analyses. In this work, we analyze the δ13C values of VOCs using thermal desorption coupled with chromatography, combustion, and isotope ratio mass spectrometry (TD-GC/C/IRMS). The measured peak shapes were of high quality and 36 compounds in a standard gas containing 58 VOCs (C5-C11) were detected. The measured δ13C varied widely, from -49.7‰ to -22.9‰, while the standard deviation of the δ13C values varied from 0.07‰ to 0.85‰ (n = 5). We then measured samples from two passenger cars in hot and cold modes, three gas stations, roadside air, and ambient air. In comparison with existing studies, the analytical precision for the 36 compounds in this study was reasonable. By comparing the δ13C values obtained from the cars and gas stations, we could identify some degree of the sources of VOCs in the roadside and ambient air samples.

  7. Stable Carbon Isotope Ratios of Toluene in the Boundary Layer and the Lower Troposphere

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Bühler, F.; Heuser, H.-P.; Knieling, P.; Koppmann, R.; Krebsbach, M.; Linke, C.; Spahn, H.

    2012-04-01

    Large amounts of Volatile Organic Compounds (VOC) are emitted into the atmosphere by various sources at the surface. Since these emissions permanently mix with each other and also are chemically processed in a large number of reactions, measurements of VOC concentrations in the troposphere are not easy to interpret. Additional measurements of stable carbon isotope ratios in VOC provide further useful information. They allow the determination of the photochemical age of the corresponding compound and, making use of the concept of the effective Kinetic Isotope Effect (KIE), to separate the effects of mixing and chemical processing. Whole air samples were taken in the boundary layer and the lower troposphere onboard a zeppelin over the Lake Constance region in late autumn 2008 and analysed in the laboratory using a GC-C-IRMS (Gas Chromatograph - Combustion - Isotope Ratio Mass Spectrometer). The GC-C-IRMS was characterised carefully to estimate the precision as well as the effect of sample humidity on the measurement results. The major ion signal was used to derive VOC mixing ratios. We present stable isotope ratios (δ13C) and mixing ratios of toluene as an example compound and apply the aforementioned concepts of interpretation. The results show that the evolution of air masses in the boundary layer was characterised mainly by mixing, whereas the air masses in the free troposphere show significant influence of chemical processing.

  8. Irradiated Xenon Isotopic Ratio Measurement for Failed Fuel Detection and Location in Fast Reactor

    NASA Astrophysics Data System (ADS)

    Ito, Chikara; Iguchi, Tetsuo; Harano, Hideki

    2009-08-01

    The accuracy of xenon isotopic ratio burn-up calculations used for failed fuel identification was evaluated by an irradiation test of xenon tag gas samples in the Joyo test reactor. The experiment was carried out using pressurized steel capsules containing unique blend ratios of stable xenon tag gases in an on-line creep rupture experiment in Joyo. The tag gas samples were irradiated to total neutron fluences of 1.6 to 4.8 × 1026 n/m2. Laser resonance ionization mass spectrometry was used to analyze the cover gas containing released tag gas diluted to isotopic ratios of 100 to 102 ppb. The isotopic ratios of xenon tag gases after irradiation were calculated using the ORIGEN2 code. The neutron cross sections of xenon nuclides were based on the JENDL-3.3 library. These cross sections were collapsed into one group using the neutron spectra of Joyo. The comparison of measured and calculated xenon isotopic ratios provided C/E values that ranged from 0.92 to 1.10. The differences between calculation and measurement were considered to be mainly due to the measurement errors and the xenon nuclide cross section uncertainties.

  9. Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

    NASA Astrophysics Data System (ADS)

    Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

    2013-12-01

    Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

  10. Disentangling effects of growth and nutritional status on seabird stable isotope ratios

    USGS Publications Warehouse

    Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

    2009-01-01

    A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

  11. Disentangling effects of growth and nutritional status on seabird stable isotope ratios.

    PubMed

    Sears, Justine; Hatch, Scott A; O'Brien, Diane M

    2009-02-01

    A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather delta(15)N and delta(13)C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing delta(15)N and delta(13)C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in delta(15)N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC delta(15)N, with chicks exhibiting lower delta(15)N when they were growing the fastest. As growth slowed, delta(15)N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted delta(15)N in chick RBCs by 0.92 per thousand. We propose that increased nitrogen-use efficiency is responsible for (15)N depletion in both growing and food-restricted chicks. delta(15)N values in RBCs of free-ranging auklets fell within a range of only 1.03 per thousand, while feather delta(15)N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in

  12. Determination of Light Water Reactor Fuel Burnup with the Isotope Ratio Method

    SciTech Connect

    Gerlach, David C.; Mitchell, Mark R.; Reid, Bruce D.; Gesh, Christopher J.; Hurley, David E.

    2007-11-01

    For the current project to demonstrate that isotope ratio measurements can be extended to zirconium alloys used in LWR fuel assemblies we report new analyses on irradiated samples obtained from a reactor. Zirconium alloys are used for structural elements of fuel assemblies and for the fuel element cladding. This report covers new measurements done on irradiated and unirradiated zirconium alloys, Unirradiated zircaloy samples serve as reference samples and indicate starting values or natural values for the Ti isotope ratio measured. New measurements of irradiated samples include results for 3 samples provided by AREVA. New results indicate: 1. Titanium isotope ratios were measured again in unirradiated samples to obtain reference or starting values at the same time irradiated samples were analyzed. In particular, 49Ti/48Ti ratios were indistinguishably close to values determined several months earlier and to expected natural values. 2. 49Ti/48Ti ratios were measured in 3 irradiated samples thus far, and demonstrate marked departures from natural or initial ratios, well beyond analytical uncertainty, and the ratios vary with reported fluence values. The irradiated samples appear to have significant surface contamination or radiation damage which required more time for SIMS analyses. 3. Other activated impurity elements still limit the sample size for SIMS analysis of irradiated samples. The sub-samples chosen for SIMS analysis, although smaller than optimal, were still analyzed successfully without violating the conditions of the applicable Radiological Work Permit

  13. 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

  14. Stable isotope ratio measurements of royal jelly samples for controlling production procedures: impact of sugar feeding.

    PubMed

    Daniele, Gaëlle; Wytrychowski, Marine; Batteau, Magali; Guibert, Sylvie; Casabianca, Hervé

    2011-07-30

    The carbon and nitrogen stable ratios of royal jelly (RJ) samples from various origins are determined using an elemental analyser linked online to an isotope ratio mass spectrometer to evaluate authenticity and adulteration. The (13)C/(12)C and (15)N/(14)N stable isotope ratios are measured in more than 500 RJs (domestic, imported and derived from feeding experiments) in order to obtain isotopic measurements that take into account seasonal, botanical and geographical effects. Authenticity intervals are established for traditional beekeeping practices, without feeding, in the range -22.48 to -27.90‰ for δ(13)C. For these samples, the δ(15)N values range from -1.58 to 7.98‰, depending on the plant sources of pollen and nectar. The δ(13)C values of the commercial samples vary from -18.54 to -26.58‰. High δ(13)C values are typical of sugar cane or corn syrups which have distinctive isotopic (13)C signatures because both plants use the C4 photosynthetic cycle, in contrast to most RJs which are derived from C3 plants. These differences in the (13)C-isotopic composition allow the detection of the addition of such sugars. RJs from traditional sources and from industrial production by sugar feeding are thus successfully distinguished. PMID:21698675

  15. Uranium isotopic ratio measurements of U3O8 reference materials by atom probe tomography.

    PubMed

    Fahey, Albert J; Perea, Daniel E; Bartrand, Jonah; Arey, Bruce W; Thevuthasan, Suntharampillai

    2016-03-01

    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 the 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. PMID:26774651

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

    SciTech Connect

    Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG; Arey, Bruce W.; Thevuthasan, Suntharampillai

    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 the 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.

  17. Proportions of convective and stratiform precipitation revealed in water isotope ratios

    NASA Astrophysics Data System (ADS)

    Aggarwal, Pradeep K.; Romatschke, Ulrike; Araguas-Araguas, Luis; Belachew, Dagnachew; Longstaffe, Frederick J.; Berg, Peter; Schumacher, Courtney; Funk, Aaron

    2016-08-01

    Tropical and midlatitude precipitation is fundamentally of two types, spatially limited and high-intensity convective or widespread and lower-intensity stratiform, owing to differences in vertical air motions and microphysical processes governing rain formation. These processes are difficult to observe or model and precipitation partitioning into rain types is critical for understanding how the water cycle responds to changes in climate. Here, we combine two independent data sets--convective and stratiform precipitation fractions, derived from the Tropical Rainfall Measuring Mission satellite or synoptic cloud observations, and stable isotope and tritium compositions of surface precipitation, derived from a global network--to show that isotope ratios reflect rain type proportions and are negatively correlated with stratiform fractions. Condensation and riming associated with boundary layer moisture produces higher isotope ratios in convective rain, along with higher tritium when riming in deep convection occurs with entrained air at higher altitudes. On the basis of our data, stable isotope ratios can be used to monitor changes in the character of precipitation in response to periodic variability or changes in climate. Our results also provide observational constraints for an improved simulation of convection in climate models and a better understanding of isotope variations in proxy archives, such as speleothems and tropical ice.

  18. 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

  19. Deuterium stable isotope ratios as tracers of water resource use: an experimental test with rock doves.

    PubMed

    McKechnie, Andrew E; Wolf, Blair O; Martínez del Rio, Carlos

    2004-07-01

    Naturally-occurring deuterium stable isotope ratios can potentially be used to trace water resource use by animals, but estimating the contribution of isotopically distinct water sources requires the accurate prediction of isotopic discrimination factors between water inputs and an animal's body water pool. We examined the feasibility of using estimates of water fluxes between a bird and its environment with a mass-balance model for the deuterium stable isotope ratio of avian body water (deltaDbody) to predict isotopic discrimination factors. Apparent fractionation and thus discrimination factors were predicted to vary with the proportion of an animal's total water losses than could be attributed to evaporative processes. To test our ability to predict isotopic discrimination, we manipulated water intake and evaporative water loss in rock doves (Columba livia) by providing them with fresh water or 0.15 M NaCl solution in thermoneutral or hot environments. After we switched the birds from drinking water with deltaD=-95 per thousand VSMOW (Vienna Standard Mean Ocean Water) to enriched drinking water with deltaD=+52 per thousand VSMOW, steady-state deltaDbody was approached asymptotically. The equilibrium deltaDbody was enriched by 10-50 per thousand relative to water inputs. After isotopic equilibrium was reached, the degree of enrichment was positively related (r2=0.34) to the fraction of total water loss that occurred by evaporation (revap/rH2O)supporting the major prediction of the model. The variation we observed in discrimination factors suggests that the apparent fractionation of deuterium will be difficult to predict accurately under natural conditions. Our results show that accurate estimates of the contribution of different water sources to a bird's body water pool require large deuterium isotopic differences between the sources. PMID:15185137

  20. Stable nitrogen isotope ratios and accumulation of various HOCs in northern Baltic aquatic food chains

    SciTech Connect

    Broman, D.; Axelman, J.; Bergqvist, P.A.; Naef, C.; Rolff, C.; Zebuehr, Y.

    1995-12-31

    Ratios of naturally occurring stable isotopes of nitrogen ({delta}{sup 15}N) can be used to numerically classify trophic levels of organisms in food chains. By combining analyses results of various HOCs (e.g. PCDD/Fs, PCBs, DDTs, HCHs and some other pesticides) the biomagnification of these substances can be quantitatively estimated. In this paper different pelagic and benthic northern Baltic food chains were studied. The {delta}{sup 15}N-data gave food chain descriptions qualitatively consistent with previous conceptions of trophic arrangements in the food chains. The different HOCs concentrations were plotted versus the {delta}{sup 15}N-values for the different trophic levels and an exponential model of the form e{sup (A+B*{delta}N)} was fitted to the data. The estimates of the constant B in the model allows for an estimation of a biomagnification power (B) of different singular, or groups of, contaminants. A B-value around zero indicates that a substance is flowing through the food chain without being magnified, whereas a value > 0 indicates that a substance is biomagnified. Negative B-values indicate that a substance is not taken up or is metabolized. The A-term of the expression is only a scaling factor depending on the background level of the contaminant.

  1. The first protocol of stable isotope ratio assessment in tumor tissues based on original research.

    PubMed

    Taran, Katarzyna; Frączek, Toma; Kamiński, Rafal; Sitkiewicz, Anna; Kobos, Jozef; Paneth, Piotr

    2015-09-01

    Thanks to proteomics and metabolomics, for the past several years there has been a real explosion of information on the biology of cancer, which has been achieved by spectroscopic methods, including mass spectrometry. These modern techniques can provide answers to key questions about tissue structure and mechanisms of its pathological changes. However, despite the thousands of spectroscopic studies in medicine, there is no consensus on issues ranging from the choice of research tools, acquisition and preparation of test material to the interpretation and validation of the results, which greatly reduces the possibility of transforming the achieved knowledge to progress in the treatment of individual patients. The aim of this study was to verify the utility of isotope ratio mass spectrometry in the evaluation of tumor tissues. Based on experimentation on animal tissues and human neoplasms, the first protocol of stable isotope ratio assessment of carbon and nitrogen isotopes in tumor tissues was established. PMID:26619108

  2. Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

    SciTech Connect

    Isselhardt, B. H.; Savina, M. R.; Kucher, A.; Gates, S. D.; Knight, K. B.; Hutcheon, I. D.

    2015-09-01

    Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured 240Pu/239Pu ratios of 0.7% and 0.58%, with precisions (95% confidence intervals) of 1.49% and 0.91%. In conclusion, the minor isotope 238Pu was also quantified despite the presence of a significant quantity of 238U in the samples.

  3. Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

    DOE PAGESBeta

    Isselhardt, B. H.; Savina, M. R.; Kucher, A.; Gates, S. D.; Knight, K. B.; Hutcheon, I. D.

    2015-09-01

    Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured 240Pu/239Pu ratios of 0.7% and 0.58%, with precisions (95% confidence intervals) of 1.49% and 0.91%. In conclusion, the minor isotope 238Pu was also quantified despite the presence ofmore » a significant quantity of 238U in the samples.« less

  4. Locally Grown, Natural Ingredients? The Isotope Ratio Can Reveal a Lot!

    PubMed

    Rossier, Joël S; Maury, Valérie; Pfammatter, Elmar

    2016-01-01

    This communication gives an overview of selected isotope analyses applied to food authenticity assessment. Different isotope ratio detection technologies such as isotope ratio mass spectrometry (IRMS) and cavity ring down spectroscopy (CRDS) are briefly described. It will be explained how δ(18)O of water contained in fruits and vegetables can be used to assess their country of production. It will be explained why asparagus grown in Valais, in the centre of the Alps carries much less heavy water than asparagus grown closer to the sea coast. On the other hand, the use of δ(13)C can reveal whether a product is natural or adulterated. Applications including honey or sparkling wine adulteration detection will be briefly presented. PMID:27198812

  5. Intercolony variability of skeletal oxygen and carbon isotope ratios of corals: temperature-controlled tank experiment and field observation

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Omata, T.; Kawahata, H.

    2005-12-01

    We conducted tank experiments in which we grew Porites spp. colonies in thermostated seawater at five temperature settings under moderate light intensity. A skeletal isotope microprofiling technique applied along the major growth axis of each colony revealed that the oxygen isotope ratios of newly deposited skeleton in most colonies remained almost constant during tank incubation. However, the oxygen isotope ratios displayed a surprisingly large intercolony variability (~1‰ at each temperature setting) although the mean slope obtained for the temperature - skeletal oxygen isotope ratio relationship was close to previous results. The variations in the oxygen isotope ratios were apparently caused by kinetic isotope effects related to variations in the skeletal growth rate rather than by species-specific variability or genetic differences within species. Carbon isotope ratios showed significantly inverse correlation with linear growth rates, suggesting a kinetic isotope control at low growth rates. We also examined oxygen and carbon isotope ratios of Porites corals collected from coral reefs of southern Ryukyu Islands, Japan. In shallow faster-growing corals, oxygen and carbon isotope ratios showed out-of-phase annual fluctuations. In contrast, in deep slower growing corals (mean annual linear extension < 4.8 mm yr1), oxygen and carbon isotope fluctuations were in phase, which has been identified as a pattern influenced by kinetic isotope effects. The slower growing corals were strongly influenced, and the faster growing corals weakly influenced, by kinetic isotope effects over metabolic isotope effects. Growth-rate-related kinetic isotope effects found in both the cultured corals and the deep slower-growing corals may be, at least partly, attributed to low light condition.

  6. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter

    NASA Astrophysics Data System (ADS)

    Moukhtar, S.; Saccon, M.; Kornilova, A.; Irei, S.; Huang, L.; Rudolph, J.

    2011-11-01

    A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyl)trifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng μl-1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry. The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m-3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m-3. In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m-3 range in rural areas to more than 200 pg m-3 in some samples from a suburban location.

  7. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  8. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  9. NITROGEN STABLE ISOTOPE RATIOS IN SPOROCARPS OF ECTOMYCORRHIZAL FUNGI: INFLUENCE OF PHYLOGENETIC AND ENVIRONMENTAL FACTORS

    EPA Science Inventory

    It has been suggested that nitrogen stable isotope ratios (expressed as delta 15-N) of fungus sporocarps, in conjunction with delta 15-N data from other ecosystem compartments, can be used to elucidate key processes in forest N-cycling. Although results of previous studies genera...

  10. PHYLOGENETIC AND ENVIRONMENTAL INFLUENCES ON NITROGEN STABLE ISOTOPE RATIOS IN SPOROCARPS OF ECTOMYCORRHIZAL FUNGI

    EPA Science Inventory

    It has been suggested that nitrogen stable isotope ratios (expressed as d15N) of fungus sporocarps, in conjunction with d15N data from other ecosystem compartments, can be used to elucidate key processes in forest N-cycling. Although results of previous studies generally support ...